JP5483811B2 - Organic solvent dispersion of composite resin and use thereof - Google Patents

Description

  The present invention relates to an organic solvent dispersion of a composite resin and its use, and more specifically, formed from a propylene / 1-butene random copolymer (A) and a copolymerizable monomer (B) or a polymer of the monomer (C). The present invention relates to an organic solvent dispersion of a composite resin comprising a composite resin and an organic solvent, and use thereof.

  Conventionally, polyolefin resins generally have high productivity and various moldability, and have many advantages such as light weight, rust prevention and impact resistance, etc. Widely used as home appliances, furniture, miscellaneous goods, building materials, etc.

  Such polyolefin resin molded products are generally nonpolar and crystalline, unlike synthetic resins having polarity typified by polyurethane resins, polyamide resins, acrylic resins and polyester resins. Therefore, it is very difficult to apply or adhere to the polyolefin resin molding using a general-purpose paint or adhesive.

  For this reason, when coating or adhering to a polyolefin resin molded product, the surface has been subjected to primer treatment or activation to improve adhesion to the surface. For example, in automotive bumpers, the surface of the bumper is etched with a halogen-based organic solvent such as trichloroethane to improve adhesion to the coating film, or after pretreatment such as corona discharge treatment, plasma treatment, or ozone treatment. However, the purpose of painting and bonding has been made.

  However, painting and adhesion using these conventionally known general-purpose paints and adhesives not only require a large amount of equipment costs, but also take a long time to implement, and the finish is not uniform, and surface treatment It was the cause of the difference in the state.

  Therefore, conventionally, as a coating composition for improving the above-mentioned problems, for example, a composition in which maleic acid is introduced into polyolefin (Japanese Patent Publication No. Sho 62-21027), or a composition mainly composed of chlorinated modified polyolefin ( Japanese Patent Publication No. 50-10916) has been proposed. However, although these are excellent in adhesion to polyolefin-based molded articles, etc., they are inferior in weather resistance, so that they are usually limited to use as a primer or in places where weather resistance is unnecessary. . Therefore, when these compositions are used and coating is performed on a place where weather resistance is required, a two-coat finish that requires complicated operations is usually required.

  For this reason, excellent adhesion to the material can be expressed without any pretreatment, and the development of a paint capable of one-coat finishing with excellent weather resistance has been developed. For example, a resin composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin (Japanese Patent Laid-Open No. 58-71966, etc.), or a coating composition comprising a hydroxyl group-containing acrylic-chlorinated polyolefin copolymer and an isocyanate compound A product (Japanese Patent Laid-Open No. 59-27968) has been proposed. However, since these contain chlorine, there is a concern about the impact on the environment.

In addition, a method of introducing an unsaturated bond into polyolefin (JP-A-1-123812 and JP-A-2-269109, etc.), a method of introducing an organic peroxide (JP-A-1-131220, etc.), and 2 A method using a functional organic peroxide (JP-A No. 64-36614, etc.) has also been proposed, and these are contrivances for improving the reactivity between the polyolefin and the radically polymerizable unsaturated monomer.

  However, in the above-described resin composition and its production method, in many cases, the reaction must be carried out at a dilute concentration due to the problem of viscosity, the graft copolymerization efficiency to polyolefin is low, and the homogeneity of the radical polymerizable unsaturated monomer is low. Since the polymer is easily formed, the obtained resin solution is very easily separated, and usually has the disadvantage that it cannot be used as it is, and the coating of these also causes stickiness. had.

  In addition, a modified polypropylene resin dispersion (JP-A 63-12651, etc.) has also been proposed for bonding between polyolefin and metal such as aluminum. However, in order to reduce the stickiness of the coating film, a raw material having a high melting point is used and there is a drawback that the heat sealing temperature is high.

In order to solve the above-mentioned problems, a solvent dispersion of a composite resin including a propylene-based elastomer and a copolymerizable monomer polymer has been proposed (International Publication No. 2004/101679 pamphlet, etc.). The solvent dispersion of the composite resin has various excellent physical properties such as spray coating without causing a separation phenomenon, but further improvement in storage stability at low temperatures is desired. It was.
Japanese Patent Publication No. 62-21027 Japanese Patent Publication No. 50-10916 JP 58-71966 A JP 59-27968 JP-A-1-123812 JP-A-2-269109 JP-A-1-131220 JP-A 64-36614 JP-A 63-12651 International Publication No. 2004/101679 Pamphlet

  The present invention has been made in view of the above-described problems of the prior art, and is an organic solvent for a composite resin that can be spray-coated without causing a separation phenomenon and that is excellent in storage stability and adhesion at low temperatures. The object is to provide a dispersion as well as its use.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the following organic resin dispersion of a composite resin is excellent in storage stability and adhesion at low temperatures, and completed the present invention.

That is, the present invention relates to the following [1] to [19].
[1] Propylene / 1-butene random copolymer (A);
at least one copolymerizable monomer (B) selected from the group consisting of a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer;
An organic solvent dispersion of a composite resin formed from the composite resin and an organic solvent,
The propylene / 1-butene random copolymer (A) is
(1) containing units derived from propylene in an amount of 60 to 90 mol% and units derived from 1-butene in an amount of 10 to 40 mol%;
(2) The triad isotacticity obtained from ¹³ C-NMR spectrum measurement is 85% or more and 97.5% or less,
(3) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is in the range of 1 to 3,
(4) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1-12 dl / g,
(5) The melting point (Tm) measured by a differential scanning calorimeter is in the range of 40 to 120 ° C.,
(6) The relationship between the melting point (Tm) and the 1-butene constituent unit content M (mol%) is
146 exp (−0.022 M) ≧ Tm ≧ 125 exp (−0.032 M)
And
The copolymerizable monomer (B) is at least one copolymer selected from the group consisting of (meth) acrylic acid esters, aromatic vinyl compounds, vinyl acetate, vinyl propionate, and α-olefins having 2 to 20 carbon atoms. An organic solvent dispersion of a composite resin comprising a functional monomer (B-1).

[2] Propylene / 1-butene random copolymer (A);
a polymer (C) of at least one copolymerizable monomer (B) selected from the group consisting of monomers having an α, β-monoethylenically unsaturated group and other copolymerizable monomers;
An organic solvent dispersion of a composite resin formed from the composite resin and an organic solvent,
The propylene / 1-butene random copolymer (A) is
(1) containing units derived from propylene in an amount of 60 to 90 mol% and units derived from 1-butene in an amount of 10 to 40 mol%;
(2) The triad isotacticity obtained from ¹³ C-NMR spectrum measurement is 85% or more and 97.5% or less,
(3) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is in the range of 1 to 3,
(4) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1-12 dl / g,
(5) The melting point (Tm) measured by a differential scanning calorimeter is in the range of 40 to 120 ° C.,
(6) The relationship between the melting point (Tm) and the 1-butene constituent unit content M (mol%) is
146 exp (−0.022 M) ≧ Tm ≧ 125 exp (−0.032 M)
And
The copolymerizable monomer (B) is at least one copolymer selected from the group consisting of (meth) acrylic acid esters, aromatic vinyl compounds, vinyl acetate, vinyl propionate, and α-olefins having 2 to 20 carbon atoms. An organic solvent dispersion of a composite resin comprising a functional monomer (B-1).

  [3] The propylene / 1-butene random copolymer (A) and the copolymerizable monomer (B) have a weight ratio of (A) / (B) = 10/90 to 90/10 [ [1] An organic solvent dispersion of the composite resin according to [1].

  [4] The propylene / 1-butene random copolymer (A) and the polymer (C) have a weight ratio of (A) / (C) = 10/90 to 90/10 [2] An organic solvent dispersion of the composite resin described in 1.

[5] A paint containing an organic solvent dispersion of the composite resin according to any one of [1] to [4].
[6] A primer containing an organic solvent dispersion of the composite resin according to any one of [1] to [4].

[7] An adhesive containing the organic solvent dispersion of the composite resin according to any one of [1] to [4].
[8] An additive containing the organic solvent dispersion of the composite resin according to any one of [1] to [4].

[9] A binder containing an organic solvent dispersion of the composite resin according to any one of [1] to [4].
[10] A film obtained from the organic solvent dispersion of the composite resin according to any one of [1] to [4].

  [11] The composite resin according to any one of [1] to [4], wherein the copolymerizable monomer (B) contains a copolymerizable monomer having active hydrogen and / or a hydroxyl group. Organic solvent dispersion.

[12] A paint containing the organic resin dispersion of the composite resin according to the above [11] and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.
[13] A primer containing an organic solvent dispersion of the composite resin according to [11] above and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.

[14] An adhesive containing the organic resin dispersion of the composite resin according to [11] above and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.
[15] An additive containing the organic resin dispersion of the composite resin according to [11] above and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.

[16] A binder containing an organic solvent dispersion of the composite resin according to [11] above and a curing agent capable of reacting with active hydrogen and / or hydroxyl groups.
[17] A film containing the organic resin dispersion of the composite resin according to [11] and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.

[18] A coating film obtained by applying the paint, primer, adhesive, additive, or binder according to any one of [5] to [9].
[19] A coating film formed by applying the paint, primer, adhesive, additive, or binder according to any one of [12] to [16].

  The organic solvent dispersion of the composite resin of the present invention can be spray-coated without causing a separation phenomenon by using a specific propylene / 1-butene random copolymer (A), and at a low temperature. Excellent storage stability and adhesion.

Hereinafter, the present invention will be specifically described.
There are two embodiments of the organic solvent dispersion of the composite resin of the present invention.
As the organic solvent dispersion of the composite resin of the first aspect (hereinafter also referred to as the organic solvent dispersion of the first composite resin), the propylene / 1-butene random copolymer (A), α, β-mono A composite resin formed from at least one copolymerizable monomer (B) selected from the group consisting of a monomer having an ethylenically unsaturated group and another copolymerizable monomer, and an organic solvent It is an organic solvent dispersion of a composite resin.

Further, as the organic solvent dispersion of the composite resin of the second aspect (hereinafter also referred to as the organic solvent dispersion of the second composite resin), the propylene / 1-butene random copolymer (A), α, β- A composite formed from a polymer (C) of at least one copolymerizable monomer (B) selected from the group consisting of a monomer having a monoethylenically unsaturated group and another copolymerizable monomer An organic solvent dispersion of a composite resin comprising a resin and an organic solvent.

The propylene / 1-butene random copolymer (A) used in the present invention is (1) 60 to 90 mol% of units derived from propylene and 10 to 40 mol of units derived from 1-butene. (2) The triad isotacticity determined from ¹³ C-NMR spectrum measurement is 85% or more and 97.5% or less, and (3) determined by gel permeation chromatography (GPC). Molecular weight distribution (Mw / Mn) in the range of 1 to 3, (4) Intrinsic viscosity measured in decalin at 135 ° C. is 0.1 to 12 dl / g, (5) Differential scanning calorimeter (6) The relationship between the melting point (Tm) and the 1-butene constituent unit content M (mol%) satisfies the following formula: Yes.

146 exp (−0.022 M) ≧ Tm ≧ 125 exp (−0.032 M)
The copolymerizable monomer (B) used in the present invention is selected from the group consisting of (meth) acrylic acid esters, aromatic vinyl compounds, vinyl acetate, vinyl propionate, and α-olefins having 2 to 20 carbon atoms. It contains at least one copolymerizable monomer (B-1).

  The organic solvent dispersion of the first composite resin of the present invention includes, for example, (i) a monomer having an α, β-monoethylenically unsaturated group and a propylene / 1-butene random copolymer (A) and A method in which at least one copolymerizable monomer (B) selected from the group consisting of other copolymerizable monomers (B) and a polymerization initiator are polymerized while feeding, and then a radical is further generated and reacted; Or (ii) at least selected from the group consisting of a propylene / 1-butene random copolymer (A), a monomer having an α, β-monoethylenically unsaturated group, and another copolymerizable monomer It can be produced by a method in which a polymerization is carried out while feeding a polymerization initiator to one kind of copolymerizable monomer (B), and then a radical is further generated to react. The organic solvent dispersion of the second composite resin of the present invention is, for example, (iii) a propylene / 1-butene random copolymer (A) and a monomer having an α, β-monoethylenically unsaturated group. And a polymer (C) of at least one copolymerizable monomer (B) selected from the group consisting of monomers and other copolymerizable monomers can be produced by a method in which radicals are generated and reacted. .

<Propylene / 1-butene random copolymer (A)>
The propylene / 1-butene random copolymer (A) used in the present invention satisfies the following (1) to (6), and preferably satisfies (7) and (8). The organic solvent dispersion of the composite resin of the present invention is excellent in storage stability and adhesion at low temperatures by using a specific propylene / 1-butene random copolymer (A).

  The propylene / 1-butene random copolymer (A) used in the present invention is (1) 60 to 90 mol%, preferably 65 to 88 mol%, more preferably 70 to 85 mol% of units derived from propylene. More preferably, the unit derived from 1-butene in an amount of 70 to 75 mol% is 10 to 40 mol%, preferably 12 to 35 mol%, more preferably 15 to 30 mol%, still more preferably 25 to 30 mol. % (However, all the structural units are 100 mol%).

  This propylene / 1-butene random copolymer (A) may contain a small amount of structural units derived from olefins other than propylene and 1-butene, such as ethylene, for example, in an amount of 10 mol% or less.

The propylene / 1-butene random copolymer (A) used in the present invention has a triad isotacticity (mm fraction) determined from (2) ¹³ C-NMR spectrum measurement of 85% or more and 97.5% or less, Preferably they are 87% or more and 97% or less, More preferably, they are 90% or more and 97% or less. In the present invention, it is important not to increase the mm fraction too much, and by providing a specific mm fraction, the melting point can be lowered with a relatively high propylene content.

The triad isotacticity (mm fraction) is an index indicating the stereoregularity of the propylene / 1-butene random copolymer (A), and can be determined as follows.
This mm fraction is defined as the ratio in which the branching directions of the methyl groups are the same when the three head-to-tail bonded propylene unit chains present in the polymer chain are represented by a surface zigzag structure. In ¹³ C-NMR spectrum.

When the mm fraction of the propylene / 1-butene random copolymer (A) is determined from the ¹³ C-NMR spectrum, as a three-chain containing propylene units specifically present in the polymer chain, (i) head- The mm fraction was measured for three chains of propylene units with tail-bonded, and (ii) three units of propylene units / butene units composed of propylene units and butene units with head-tail bonds and the second unit being propylene units. The

The mm fraction is determined from the peak intensity of the side chain methyl group of the second unit (propylene unit) in these three chains (i) and (ii). This will be described in detail below.
The ¹³ C-NMR spectrum of the propylene / 1-butene random copolymer (A) is hexachlorobutadiene containing a small amount of deuterated benzene using the propylene / 1-butene random copolymer (A) as a lock solvent in the sample tube. After complete dissolution, it is measured by proton complete decoupling method at 120 ° C. The measurement conditions are a flip angle of 45 ° and a pulse interval of 3.4 T1 or more (T1 is the longest value of the spin lattice relaxation time of the methyl group). Since T1 of the methylene group and methine group is shorter than that of the methyl group, the recovery of the magnetization of all the carbon in the sample is 99% or more under this condition. In the chemical shift, the methyl group carbon peak of the third unit of propylene units having 5 head-to-tail bonds (mmmm) based on tetramethylsilane was set to 21.593 ppm, and the other carbon peaks were based on this.

Of the ¹³ C-NMR spectrum of the propylene / 1-butene random copolymer (A) thus measured, the methyl carbon region (about 19.5 to 21.9 ppm) in which the side chain methyl group of the propylene unit is observed. ) Are classified into a first peak region (about 21.0 to 21.9 ppm), a second peak region (about 20.2 to 21.0 ppm), and a third peak region (about 19.5 to 20.2 ppm). The

  In each of these regions, a side chain methyl group peak of the second unit (propylene unit) in the trimolecular chain (i) and (ii) having head-to-tail bonds as shown in Table 1 is observed.

  In Table 1, P represents a structural unit derived from propylene, and B represents a structural unit derived from 1-butene. Of the head-to-tail three-linkage (i) and (ii) shown in Table 1, (i) methyl groups for PPP (mm), PPP (mr), and PPP (rr), in which all three chains are composed of propylene units The direction is illustrated in a surface zigzag structure below, but (ii) mm, mr, and rr bonds of three-chain (PPB, BPB) containing butene units conform to this PPP.

  In the first region, the methyl group of the second unit (propylene unit) in the mm-bonded PPP, PPB, BPB3 chain resonates. In the second region, the methyl group of the second unit (propylene unit) in the mr-bonded PPP, PPB, BPB3 chain and the methyl group of the second unit (propylene unit) in the rr-bonded PPB, BPB3 chain are resonant. To do.

In the third region, the methyl group of the second unit (propylene unit) of the rr-bonded PPP3 chain resonates. Therefore, the triad isotacticity (mm fraction) of the propylene / 1-butene random copolymer (A) is as follows: (i) 3 units of propylene units bonded to head-to-tail, or (ii) propylene units bonded to head-to-tail And 3 units of propylene / butene comprising a propylene unit in the second unit, and a ¹³ C-NMR spectrum (hexachlorobutadiene) for the side chain methyl group of the second unit propylene unit in the third chain. 21.0 to 21.9 ppm (first region) when the total area of the peak appearing in 19.5 to 21.9 ppm (methyl carbon region) is defined as 100% when measured with a solution and tetramethylsilane ) Is obtained from the following formula (1) as a ratio (percentage) of the area of the peak appearing.

  As described above, the propylene / 1-butene random copolymer (A) used in the present invention has a mm fraction of 85% or more and 97.5% or less, preferably 87% or more and 97% or less, as described above. More preferably, it is 90% or more and 97% or less. In the present invention, it is important not to increase the mm fraction too much, and by providing a specific mm fraction, the melting point can be lowered with a relatively high propylene content. The propylene / 1-butene random copolymer (A) has the following structures (iii), (iv) and (v) in addition to the above-described three-chain (i) and (ii) bonded to the head. And a peak derived from the side chain methyl group of the propylene unit by such other bonds is also in the above methyl carbon region (19.5 to 21). .9 ppm).

  Among the methyl groups derived from the structures (iii), (iv) and (v), the methyl group carbon A and the methyl group carbon B resonate at 17.3 ppm and 17.0 ppm, respectively. The peak based on B does not appear in the first to third regions (19.5 to 21.9 ppm). Furthermore, since carbon A and carbon B are not involved in the propylene trilinkage based on the head-to-tail bond, it is not necessary to consider in the calculation of the triad isotacticity (mm fraction).

The peak based on the methyl group carbon C, the peak based on the methyl group carbon D, and the peak based on the methyl group carbon D ′ appear in the second region, and the peak based on the methyl group carbon E and the peak based on the methyl group carbon E ′ are Appears in the third region.

  Therefore, the 1st to 3rd methyl carbon regions include PPE-methyl group (side chain methyl group in propylene-propylene-ethylene chain) (around 20.7 ppm), EPE-methyl group (side in ethylene-propylene-ethylene chain). (Chain methyl group) (around 19.8 ppm), peaks based on methyl group C, methyl group D, methyl group D ′, methyl group E, and methyl group E ′ appear.

  Thus, in the methyl carbon region, peaks of methyl groups that are not based on the head-to-tail bond three linkages (i) and (ii) are also observed. It is corrected as follows.

  The peak area based on the PPE-methyl group can be obtained from the peak area of the PPE-methine group (resonant at around 30.6 ppm), and the peak area based on the EPE-methyl group is determined based on the EPE-methine group (around 32.9 ppm). Resonance) peak area.

The peak area based on the methyl group C can be determined from the peak area of the adjacent methine group (resonance near 31.3 ppm). The peak area based on the methyl group D can be determined from ½ of the sum of the peak areas of the peaks based on the αβ methylene carbon of the structure (iv) (resonance at around 34.3 ppm and around 34.5 ppm). The peak area based on the group D ′ is a peak based on the methine group adjacent to the methyl group of the methyl group E ′ of the structure (v) (33.
(Resonance at around 3 ppm).

The peak area based on the methyl group E can be obtained from the peak area of the adjacent methine carbon (resonant at around 33.7 ppm), and the peak area based on the methyl group E ′ is determined at the adjacent methine carbon (around 33.3 ppm). Resonance) peak area.

  Therefore, by subtracting these peak areas from the total peak areas of the second region and the third region, it is possible to determine the peak area of the methyl group based on the head-to-tail three-linked propylene units (i) and (ii). .

  As described above, the peak area of the methyl group based on the three-chain (i) and (ii) propylene units bonded head-to-tail can be evaluated, and the mm fraction can be determined according to the above formula.

Each carbon peak in the spectrum can be assigned with reference to literature (Polymer, 30, 1350 (1989)).
The propylene / 1-butene random copolymer (A) used in the present invention preferably has (3) a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) in the range of 1 to 3. It is 1.9 to 2.5 more preferably from 1.8 to 3.0.

  The propylene / 1-butene random copolymer (A) used in the present invention has (4) an intrinsic viscosity of 0.1 to 12 dl / g, preferably 0.5 to 10 dl / g, measured at 135 ° C. in decalin. More preferably, it is 1-5 dl / g.

  The propylene / 1-butene random copolymer (A) used in the present invention has (5) a melting point (Tm) measured by a differential scanning calorimeter of 40 to 120 ° C., preferably 50 to 100 ° C., more preferably. 55-90 ° C.

The propylene / 1-butene random copolymer (A) used in the present invention comprises (6) the above melting point (
Tm) and the 1-butene constituent unit content M (mol%) is 146exp (−0.022M) ≧ Tm ≧ 125exp (−0.032M)
Preferably 146 exp (−0.024 M) ≧ Tm ≧ 125 exp (−0.032 M)
More preferably, 146exp (−0.0265M) ≧ Tm ≧ 125exp (−0.032M)
It is. When such a relationship between the melting point and the butene content is satisfied, the melting point can be lowered with a relatively high propylene content, whereby a high crystallization rate can be obtained even at a low melting point.

  The propylene / 1-butene random copolymer (A) used in the present invention is preferably (7) a crystal measured at 45 ° C. of the propylene / 1-butene random copolymer (A) when the melting point is 75 ° C. or lower. The crystallization rate (1/2 crystallization time) is 10 minutes or less, more preferably 7 minutes or less.

  The propylene / 1-butene random copolymer (A) used in the present invention is preferably a parameter B value indicating the randomness of the copolymer monomer chain distribution of (8) propylene / 1-butene random copolymer (A). 0.9 to 1.3, more preferably 0.95 to 1.25, and particularly preferably 0.95 to 1.2.

  This parameter B value is proposed by Coleman et al. (BD Cole-man and TG Fox, J. Polym. Sci., Al, 3183 (1963)) and is defined as follows.

B = P ₁₂ / (2P ₁ · P ₂ )
Here, P ₁ and P ₂ are the first monomer and second monomer content fractions, respectively, and P ₁₂ is the ratio of (first monomer)-(second monomer) linkage in the chain in all two molecules.

The B value is in accordance with Bernoulli statistics when 1, and the copolymer is block-like when B <1, is alternating when B> 1, and is a cross-copolymer when B = 2. .
The propylene / 1-butene random copolymer (A) used in the present invention is a heterogeneous bond unit (position irregular unit) based on 2,1-insertion or 1,3-insertion of propylene present in the propylene chain. May have a small amount of structure containing.

During polymerization, propylene is usually 1,2-inserted (methylene side is bound to the catalyst) to form a head-to-tail coupled propylene chain as described above. May be inserted. 2,1-inserted and 1,3-inserted propylene form regioregular units as shown in structures (iii), (iv) and (v) in the polymer. As for the proportion of 2,1-insertion and 1,3-insertion of propylene in the polymer structural unit, refer to Polymer, 30, 1350 (1989) using the ¹³ C-NMR spectrum in the same manner as the stereoregularity described above. Can be obtained from the following equation.

  The ratio of position irregular units based on 2,1-insertion of propylene can be obtained from the following formula.

In addition, when it is difficult to obtain the area of Iαβ or the like directly from the spectrum due to the overlap of peaks, it can be corrected with a carbon peak having a corresponding area.
In the propylene / 1-butene random copolymer (A) used in the present invention, heterogeneous bond units based on 2,1-insertion of propylene present in the propylene chain obtained as described above are contained in all propylene structural units. It may be contained in an amount of 0.01% or more, specifically about 0.01 to 1.0%.

  Moreover, the ratio of the position irregular unit based on the 1,3-insertion of propylene of the propylene / 1-butene random copolymer (A) can be obtained from a βγ peak (resonance at around 27.4 ppm).

The propylene / 1-butene random copolymer (A) used in the present invention may have a heterogeneous bond ratio based on 1,3-insertion of propylene of 0.05% or less.
The propylene / 1-butene random copolymer (A) used in the present invention as described above can be produced by the method described in WO 2004/088775.

<At least one copolymerizable monomer (B) selected from the group consisting of a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer>
Listed below are at least one copolymerizable monomer (B) selected from the group consisting of monomers having an α, β-monoethylenically unsaturated group and other copolymerizable monomers used in the present invention. .

  Examples of the monomer having an α, β-monoethylenically unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylic esters such as phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate Hydroxyl group-containing vinyls such as relate, 2-hydroxypropyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl acrylate; acrylic acid, methacrylic acid, maleic acid, itaconic acid, Carboxy group-containing vinyls such as ω-carboxy-polycaprolactone monoacrylate and phthalic acid monohydroxyethyl acrylate; monoesterified products of these carboxyl group-containing vinyls; epoxies such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate Group-containing vinyls; isocyanate group-containing vinyls such as vinyl isocyanate and isopropenyl isocyanate; styrene, α-methylstyrene, vinyltoluene, and t-butyl Aromatic vinyls such as rustyrene; other (meth) acrylonitrile, vinyl acetate, vinyl propionate, (meth) acrylamide, methylol (meth) acrylamide, and α-olefin having 2 to 20 carbon atoms. In addition, macromonomers having the above-mentioned monomer or copolymer thereof in the segment and having a vinyl group at the terminal can also be used. Commercial products such as FM-3 (manufactured by Daicel Chemical Industries, Ltd.) can also be used.

Examples of other copolymerizable monomers include carboxylic anhydrides such as maleic anhydride and citraconic anhydride.
The copolymerizable monomer (B) used in the present invention is at least selected from the group consisting of (meth) acrylic acid esters, aromatic vinyl compounds, vinyl acetate, vinyl propionate, and α-olefins having 2 to 20 carbon atoms. 1 type of copolymerizable monomer (B-1) is included.

Moreover, description like the methyl (meth) acrylate described here shows methyl acrylate and methyl methacrylate.
As the copolymerizable monomer (B), a monomer having an α, β-monoethylenically unsaturated group is preferably used. It is also possible to use a monomer having an α, β-monoethylenically unsaturated group as a main component and other copolymerizable monomers.

  The copolymerizable monomer (B) used in the present invention preferably contains 100 to 70 parts by weight, more preferably 100 to 80 parts by weight of a monomer having an α, β-monoethylenically unsaturated group. The polymerizable monomer is preferably contained in an amount of 0 to 30 parts by weight, more preferably 0 to 20 parts by weight (provided that the monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers are included. The total with the mass is 100 parts by weight).

Further, when the total amount of the copolymerizable monomer (B) is 100 parts by weight, it is selected from the group consisting of (meth) acrylic acid ester, aromatic vinyl compound, vinyl acetate, vinyl propionate, and α-olefin having 2 to 20 carbon atoms. At least one copolymerizable monomer (B-1) selected
Is usually 100 to 50 parts by weight, preferably 100 to 60 parts by weight, more preferably 100 to 70 parts by weight.

<Polymer (C)>
The polymer (C) used for the organic solvent dispersion of the second composite resin of the present invention is obtained by copolymerizing the copolymerizable monomer (B).

It does not specifically limit as a polymerization method, Well-known methods, such as melt polymerization and suspension polymerization, are mentioned.
<Organic solvent dispersion of first composite resin>
The organic solvent dispersion of the first composite resin of the present invention comprises the above-mentioned propylene / 1-butene random copolymer (A), a monomer having an α, β-monoethylenically unsaturated group, and other copolymers. An organic solvent dispersion of a composite resin formed of at least one copolymerizable monomer (B) selected from the group consisting of possible monomers and an organic solvent.

  The organic solvent dispersion of the first composite resin of the present invention includes, for example, (i) a monomer having an α, β-monoethylenically unsaturated group and a propylene / 1-butene random copolymer (A) and A method in which at least one copolymerizable monomer (B) selected from the group consisting of other copolymerizable monomers (B) and a polymerization initiator are polymerized while feeding, and then a radical is further generated and reacted; Or (ii) at least selected from the group consisting of a propylene / 1-butene random copolymer (A), a monomer having an α, β-monoethylenically unsaturated group, and another copolymerizable monomer It can be produced by a method in which a polymerization is carried out while feeding a polymerization initiator to one type of copolymerizable monomer (B), and then a radical is further generated to react.

The propylene / 1-butene random copolymer (A) used in the present invention is selected from the group consisting of a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer. The ratio with the at least one copolymerizable monomer (B) is usually (A) / (B) = 10/90 to 90/10, preferably (A) / (B) = 10/90 in weight ratio. ~ 80/20.

Examples of the organic solvent used in the production method of (i) and (ii) above and the organic solvent contained in the organic solvent dispersion of the composite resin of the present invention include aromatic hydrocarbons such as xylene, toluene, and ethylbenzene; Aliphatic hydrocarbons such as hexane, heptane, octane, and decane; Alicyclic hydrocarbons such as cyclohexane, cyclohexene, and methylcyclohexane; Ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Examples thereof include ester systems such as ethyl ether acetate and 3-methoxybutyl acetate; ketone systems such as methyl ethyl ketone and methyl isobutyl ketone, and a mixture of two or more of these may be used. Commercial products such as Shellsol TG (manufactured by Shell Japan Co., Ltd.) can also be used. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and aliphatic hydrocarbons and alicyclic hydrocarbons can be preferably used. The amount of the organic solvent can be used in such a range that the nonvolatile content when the propylene / 1-butene random copolymer (A) is dissolved in the organic solvent is 5 to 60% by weight.

Examples of the polymerization initiator used in the production method of (i) and (ii) above include di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and dicumyl peroxide. , Organic peroxides such as lauroyl peroxide, tert-butylperoxybenzoate, and cumene hydroperoxide; azobisisobutyronitrile, 4,4′-azobis (4-cyanopentanoic acid), and 2,2 ′ -Azobis (2-methyl-N- (2-hydroxyethyl) propioamide)
An azo compound such as These can be used alone or in combination of two or more.

  After the polymerization of the propylene / 1-butene random copolymer (A) and the copolymerizable monomer (B) as in the production methods (i) and (ii) above, the reaction is performed by further generating radicals. As the radical generating method in this case, a known method such as a method of irradiating light in the presence of a photopolymerization initiator or a method of adding an organic peroxide can be used.

Examples of the photopolymerization initiator include benzophenone, diacetyl, benzyl, benzoin, 2-methylbenzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone. 2-hydroxy-2-methylpropiophenone, 2-chlorobenzophenone, p-dimethylaminopropiophenone, p-dimethylaminoacetophenone, p, p'-bisdiethylaminobenzophenone, 3,3'-4,4'- Tetra-benzophenone, Michler's ketone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Carbonyls such as benzyl dimethyl ketal and methyl benzoyl formate; Sulfides such as diphenyl disulfide, dibenzyl disulfide, and tetramethyl thiuram monosulfide; Quinones such as benzoquinone, anthraquinone, chloroanthraquinone, ethyl anthraquinone, and butyl anthraquinone; Although thioxanthones, such as thioxanthone, 2-methyl thioxanthone, and 2-chloro thioxanthone, are mentioned, you may use these individually by 1 type or in combination of 2 or more types.

  Examples of these photopolymerization initiators include amines such as triethylamine, trimethylamine, triethanolamine, dimethylaminoethanol, pyridine, quinoline, and trimethylbenzylammonium chloride; allylphosphines such as triphenylphosphine; β- A thiol ether such as thiodiglycol may be used in combination.

  The amount of the photopolymerization initiator used is usually 0.01 to 10 weights with respect to 100 parts by weight of the total weight of the propylene / 1-butene random copolymer (A) and the copolymerizable monomer (B). When used in an amount of 0.1 part by weight, more preferably in the range of 0.1 to 5 parts by weight, a great effect on stability appears.

  Examples of the organic peroxide include di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, and benzoyl peroxide having a tert-butyl group and / or a benzyl group in the molecule. , Dicumyl peroxide, tert-butyl peroxybenzoate, lauroyl peroxide, and cumene hydroperoxide. These can be used alone or in combination of two or more.

  In the present invention, among the above-described organic peroxides, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate are more preferably used. That is, the organic peroxide having a tert-butyl group and / or a benzyl group in the molecule has a relatively high hydrogen abstraction ability, and has an effect of improving the graft copolymerization efficiency with the polyolefin, and the organic solvent of the resulting composite resin The dispersion is less likely to cause separation.

  The amount of the organic peroxide used is usually 2 to 50 parts by weight based on 100 parts by weight of the total weight of the propylene / 1-butene random copolymer (A) and the copolymerizable monomer (B). Preferably, a large effect appears in stability when used in the range of 3 to 30 parts by weight. It is preferable to add the above-mentioned organic peroxide in small amounts as much as possible, or to add small amounts in small portions.

  In producing the organic solvent dispersion of the composite resin, at least one selected from the group consisting of oils and fats, oils and fats derivatives, epoxy resins, and polyester resins can be used as the third component.

Examples of the fats and oils used as the third component include linseed oil, soybean oil, castor oil, and purified products thereof.
Derivatives of fats and oils used as the third component include, for example, a fatty acid (fatty acid) modified with a polybasic acid such as phthalic anhydride and a polyhydric alcohol such as glycerin, pentaerythritol, and ethylene glycol as a skeleton. Short oil alkyd resin, medium oil alkyd resin, long oil alkyd resin, etc., or rosin modified alkyd resin, phenol modified alkyd resin, epoxy modified alkyd resin modified with natural resin, synthetic resin and polymerizable monomer, acrylic Alkyd resin and urethane-modified alkyd resin.

  Examples of the epoxy resin used as the third component include an epoxy resin obtained by glycidyl etherification of bisphenol A, bisphenol F, and novolak; and an epoxy resin obtained by adding propylene oxide or ethylene oxide to bisphenol A to form glycidyl ether. Can do. Moreover, you may use the amine modified epoxy resin etc. which added the polyfunctional amine to the epoxy group. Furthermore, for example, an aliphatic epoxy resin, an alicyclic epoxy resin, and a polyether-based epoxy resin can be mentioned.

  The polyester resin used as the third component is a polycondensation product of a carboxylic acid component and an alcohol component. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, succinic acid, and glutaric acid. Polycarboxylic acids such as adipic acid, azelaic acid, 1,10-decanedicarboxylic acid, cyclohexanedicarboxylic acid, trimellitic acid, maleic acid, and fumaric acid; lower alcohol esters thereof; hydroxycarboxylic acids such as paraoxybenzoic acid A monovalent carboxylic acid such as benzoic acid can be used, and two or more kinds can be used in combination.

Examples of the alcohol component include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 10-decanediol, 3-methyl-pentanediol, 2,2′-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin , Pentaerythritol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, and propylene oxide adduct of hydrogenated bisphenol A can be used. It is also possible to use more than one.

  Moreover, the resin containing a polymerizable unsaturated bond in a molecule | numerator obtained by adding the carboxylic anhydride which has a polymerizable unsaturated bond in a molecule | numerator to the said polyester resin which has a hydroxyl group can also be used.

  The third component can be used alone or in combination of two or more. Further, it can be added while being fed into the reactor, or it can be first charged into the reactor and used. The amount of the third component added is usually 0.5 to 60 parts by weight, preferably 2 to 40 parts by weight with respect to 100 parts by weight of the composite resin component.

<Organic solvent dispersion of second composite resin>
The organic solvent dispersion of the second composite resin of the present invention comprises the above-mentioned propylene / 1-butene random copolymer (A), a monomer having an α, β-monoethylenically unsaturated group, and other copolymers. An organic solvent dispersion of a composite resin formed from a polymer (C) of at least one copolymerizable monomer (B) selected from the group consisting of possible monomers, and an organic solvent is there.

  The organic solvent dispersion of the second composite resin of the present invention includes, for example, (iii) a propylene / 1-butene random copolymer (A), a monomer having an α, β-monoethylenically unsaturated group, and In addition, the polymer (C) of at least one copolymerizable monomer (B) selected from the group consisting of monomers that can be copolymerized can be produced by a method of generating a radical and performing a reaction.

The propylene / 1-butene random copolymer (A) used in the present invention is selected from the group consisting of a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer. The ratio of at least one copolymerizable monomer (B) to polymer (C) is usually (A) / (C) = 10/90 to 90/10, preferably (A) / ( C) = 10/90 to 80/20.

As the organic solvent used in the organic solvent dispersion of the second composite resin, the same organic solvent as that used in the organic solvent dispersion of the first composite resin can be used.
The radical generating method in the case of reacting propylene / 1-butene random copolymer (A) and polymer (C) by generating radicals is the same as the organic solvent dispersion of the first composite resin described above. As the photopolymerization initiator and organic oxide that can be used and can be used, the same organic solvent dispersion of the first composite resin can be used.

  The amount of the photopolymerization initiator used is usually 0.01 to 10 parts by weight with respect to 100 parts by weight of the total weight of the propylene / 1-butene random copolymer (A) and the polymer (C). More preferably, a great effect on the stability appears when used in the range of 0.1 to 5 parts by weight.

The amount of the organic peroxide used is usually 2 to 50 parts by weight, more preferably 100 parts by weight of the total weight of the propylene / 1-butene random copolymer (A) and the polymer (C). 3 to
When used in the range of 30 parts by weight, a great effect on stability appears.

Moreover, in producing the organic solvent dispersion of the composite resin, the same third component as the organic solvent dispersion of the first composite resin can be used.
In addition, when introduce | transducing a 3rd component, the method of mixing and using for a copolymerizable monomer (B) is preferable.

The organic solvent dispersion of the first and second composite resins of the present invention may include not only those in which the composite resin is dispersed in various organic solvents, but also those in which the composite resin is partially dissolved.
Moreover, the organic solvent dispersion of the composite resin can be used as an organic solvent dispersion of a composite resin dissolved or dispersed in an arbitrary organic solvent after removing the organic solvent.

  Of the copolymerizable monomer (B) that is a constituent unit of the composite resin contained in the organic resin dispersion of the composite resin of the present invention, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, acrylic acid, methacrylic acid, etc. When a compound having active hydrogen and / or hydroxyl group is used, it can be used together with a curing agent capable of reacting with active hydrogen and / or hydroxyl group. For example, by mixing a curing agent having an isocyanate group in the molecule, which is one of the curing agents capable of reacting with active hydrogen and / or hydroxyl groups, it can be used as a paint, primer, and adhesive having a urethane bond. it can.

  Examples of the curing agent having an isocyanate group in the molecule capable of reacting with active hydrogen and / or a hydroxyl group include aromatic diene such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate. Isocyanates; aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate and dicyclohexylmethane diisocyanate One or more isocyanate compounds and dihydric alcohols such as ethylene glycol, propylene glycol, xylylene glycol and butylene glycol, or glycerin and trimethylo Adducts with polyhydric alcohols such as propane and trihydric alcohols such as trimethylolethane, or adducts with low molecular weight polyester resins having functional groups capable of reacting with isocyanate groups or water; A polymer in which isocyanate groups are blocked with a known blocking agent such as a lower monohydric alcohol or methyl ethyl ketoxime can be used. Also in the case of using an isocyanate prepolymer, for example, an external catalyst such as dibutyltin dilaurate or triethylamine can be added.

  And a resin synthesized from at least one of melamine, urea, benzoguanamine, glycoluril and the like and formaldehyde, for example, a methylol group by a lower alcohol such as methanol, ethanol, propanol, isopropanol, butanol, and isobutanol. An amino resin obtained by alkyl etherification of one part or all of the above can also be used as a curing agent.

Commercial products such as D-177HN (manufactured by Mitsui Takeda Chemical Co., Ltd., product name) can also be used.
The organic resin dispersion of the composite resin of the present invention and the curing agent capable of reacting with active hydrogen and / or hydroxyl groups can be used in any ratio.

When the curing agent capable of reacting with active hydrogen and / or a hydroxyl group is a curing agent having an isocyanate group, the equivalent ratio of the active hydrogen and / or hydroxyl group to the isocyanate group is 0.5: 1.0 to The range of 1.0: 0.5 is preferable, and the range of 0.8: 1.0 to 1.0: 0.8 is more preferable.

  When the curing agent capable of reacting with active hydrogen and / or a hydroxyl group is an amino resin, the weight ratio of the composite resin organic solvent dispersion / amino resin solid of the present invention is in the range of 95/5 to 20/80. In the range of 90/10 to 60/40 is more preferable.

The mixture of the curing agents described above can be applied and cured as it is, but a reactive catalyst can be used in combination as required.
The organic resin dispersion of the composite resin of the present invention obtained above or the organic solvent dispersion of the composite resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group, if necessary, Organic pigments such as azo pigments and phthalocyanine blue; dyes such as azo dyes and anthraquinone dyes; colorants such as inorganic pigments such as titanium oxide, molybdenum, and carbon black; antioxidants, weathering stabilizers, and heat resistance inhibitors Anti-foaming agents, thickeners, dispersants, surfactants, fungicides, antibacterial agents, antiseptics, catalysts, fillers, waxes, antiblocking agents, plasticizers, leveling agents, etc. It can be included.

  The coating method of the organic resin dispersion of the composite resin of the present invention, or the mixture of the organic resin dispersion of the composite resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is not particularly limited, It is suitable to carry out by spray application, for example, spraying can be performed on the surface to be coated with a spray gun. The application can usually be easily performed at room temperature, and the drying method after application is not particularly limited, and can be dried by an appropriate method such as natural drying or forced heating drying.

  In addition, the organic solvent dispersion of the composite resin of the present invention, or the organic solvent dispersion of the composite resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group, has characteristics such as polyethylene, polypropylene, etc. Polyolefins, ethylene-propylene copolymers, ethylene-butene copolymers, propylene-butene copolymers, molded articles made of olefin copolymers such as ethylene-propylene-butene copolymers, and polypropylene and rubber components The molded article, polyamide resin, unsaturated polyester, polycarbonate, epoxy resin, urethane resin, steel sheet, electrodeposition-treated steel sheet, and the like can be suitably used as paints, primers, and adhesives.

  And the organic solvent dispersion of the composite resin of the present invention, or the mixture of the organic solvent dispersion of the composite resin of the present invention and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group, As an adhesive or heat sealant between polyolefins or between metal and polyolefin, the coating film has no stickiness and exhibits excellent adhesion performance and adhesion performance. In heat sealing, the organic solvent dispersion of the composite resin of the present invention exhibits its performance at a low temperature and is excellent in storage stability at a low temperature. These can also be used as an adhesive for PTP packaging and an adhesive for laminating.

  In addition, when using the organic resin dispersion of the composite resin of the present invention or a mixture of the organic solvent dispersion of the composite resin of the present invention and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group as a paint, In addition to the above, thermoplastic acrylic resin paints, thermosetting acrylic resin paints, acrylic-modified alkyd resin paints, epoxy resin paints, polyurethane resin paints, melamine resin paints, and the like can be mixed for use.

The organic resin dispersion of the composite resin of the present invention or the organic solvent dispersion of the composite resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is a urethane paint, polyester paint, melamine paint, It can be used as a paint mainly composed of an epoxy paint or the like, or as an additive for an adhesive. These additives can improve the adhesion to the surface of various objects to be coated and can form a coating film having excellent sharpness.

  The organic solvent dispersion of the composite resin of the present invention obtained above or the organic solvent dispersion of the composite resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is an azo pigment and phthalocyanine blue. Organic pigments such as azo dyes, dyes such as azo dyes and anthraquinone dyes, colorants such as inorganic pigments such as titanium oxide, molybdenum, and carbon black, and aluminum oxide, calcium carbonate, calcium hydroxide, magnesium hydroxide, silica, and titanium It can be used as a binder resin for inorganic chemicals such as barium acid.

  An organic solvent dispersion of the composite resin of the present invention obtained above or a mixture of the organic solvent dispersion of the composite resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is applied to a release film or the like. The film obtained by processing and peeling is excellent in flexibility, impact resistance, stretchability, transparency, gloss, blocking resistance, and design, so it is suitable for clothing, various packaging materials, medical instruments, and sanitary hygiene products. It can be used for various molded products, display panel surface members, optical materials and the like. Further, the light transmission can be controlled by expansion and contraction, and the transmitted light can be scattered, so that it can be used as an optical material such as a light shielding film and a light amount control film.

  Further, the organic solvent dispersion of the composite resin of the present invention obtained above or the organic solvent dispersion of the composite resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is a strippable paint. It can also be used as a primer for traffic paint.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
<Physical property measurement method>
In the present invention, each physical property was measured as follows.

(1-butene content)
^It calculated | required using < ¹³ > C-NMR.
(Intrinsic viscosity [η])
Measured in decalin at 135 ° C. and expressed in dl / g.

(Molecular weight distribution (Mw / Mn))
The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore.

The separation column is TSK GNH HT, the column size is 27 mm in diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries) and BHT ( (Takeda Pharmaceutical Co., Ltd.) was used at 0.025% by weight, moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as the detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

(B value)
B value is a ¹³ C-NMR spectrum of a sample in which about 200 mg of copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.
The measurement frequency is 25.05 MHz, the spectrum width is 1500 Hz, the filter width is 1500 Hz, the pulse repetition time is 4.2 sec, and the number of integrations is 2000 to 5000. From this spectrum, P ₁ , P ₂ , P ₁₂ (P ₁ was calculated by determining the ethylene content fraction, P ₂ being the 1-butene content fraction, and P ₁₂ being the ratio of (ethylene)-(1-butene) linkages in all bimolecular linkages).

(Triad Isotactic City)
The ¹³ C-NMR spectrum was measured with a hexachlorobutadiene solution (based on tetramethylsilane), and the area of the peak appearing at 21.0 to 21.9 ppm relative to the total area (100%) of the peak appearing at 19.5 to 21.9 ppm. The ratio (%) was obtained.

(Percentage of heterogeneous bonds based on 2,1-insertion)
Polymer, 30, 1350 (1989) was used as a reference, and was determined using the ¹³ C-NMR spectrum by the method described above.

(Melting point (Tm))
About 5 mg of sample is packed in an aluminum pan, heated to 200 ° C. at 10 ° C./minute, held at 200 ° C. for 5 minutes, then cooled to room temperature at 20 ° C./minute, and then endothermic when heated at 10 ° C./minute. Obtained from the curve. For the measurement, a DSC-7 type apparatus manufactured by Perkin Elmer was used.

(Crystallinity)
It was determined by X-ray diffraction measurement of a 1.0 mm thick press sheet that had passed at least 24 hours after molding.

(Crystallization speed)
Using the DSC apparatus, the ½ crystallization time at 45 ° C. was determined.
<Production Example 1 (synthesis of PBR-1)>
In a 2000 ml polymerization apparatus sufficiently purged with nitrogen, 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 raised to 70 ° C. with propylene. Pressurized to 0.7 MPa. Next, a toluene solution in which 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem) in contact with aluminum were contacted. Was added to the inside of 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 obtained polymer was 9.2 g. The melting point of the polymer was 80.6 ° C., and the intrinsic viscosity [η] was 1.18 dl / g. Table 2 shows the measured physical properties of the obtained polymer.

<Production Example 2 (synthesis of PBR-2)>
817 ml of hexane, 50 g of 1-butene, dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride and diphenylmethylene (3-tert-butyl-5-methylcyclopentadiene) Polymerization was carried out in the same manner as in Production Example 1 except that it was changed to (enyl) 2,7-di-tert-butylfluorenylzirconium dichloride. The obtained polymer was 11.5 g. Further, the melting point of the polymer was 86.3 ° C., and the intrinsic viscosity [η] was 2.11 dl / g. Table 2 shows the measured physical properties of the obtained polymer.

<Production Example 3 (synthesis of PBR-3)>
Polymerization was carried out in the same manner as in Production Example 1, except that 800 ml of hexane was charged, 120 g of 1-butene was changed to 60 ° C. The obtained polymer was 10.8 g. Further, the melting point of the polymer was 69.0 ° C., and the intrinsic viscosity [η] was 2.06 dl / g. The physical properties measured for the obtained polymer are shown in Table 2. <Production Comparative Example 1 (synthesis of PBR-C1)>
A 2 liter autoclave thoroughly purged with nitrogen is charged with 830 ml of hexane and 100 g of 1-butene, 1 mmol of triisobutylaluminum is added, the temperature is raised to 70 ° C., and propylene is supplied to a total pressure of 0.7 MPa. Manufactured except that 1 mmol of aluminum and a titanium catalyst supported on magnesium chloride are added to 0.005 mmol in terms of Ti atoms, and propylene is continuously supplied to carry out polymerization for 30 minutes while maintaining the total pressure at 0.7 MPa. The same post-polymerization treatment as in Example 1 was performed.

  The obtained polymer was 33.7 g. The melting point of the polymer was 110.0 ° C., and the intrinsic viscosity [η] was 1.91 dl / g. Table 3 shows the measured physical properties of the obtained polymer.

<Production Comparative Example 2 (synthesis of PBR-C2)>
900 ml of hexane and 60 g of 1-butene were added, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., propylene was supplied to bring the total pressure to 0.7 MPa, methylaluminoxane 0.30 mmol, rac-dimethylsilylene- Bis {1- (2-methyl-4-phenyl-1-indenyl)} zirconium dichloride is added in an amount of 0.001 mmol in terms of Zr atoms, and propylene is continuously supplied to keep the total pressure at 0.7 MPa. The post-polymerization treatment was performed in the same manner as in Production Example 1 except that the polymerization was performed for 1 minute.

  The obtained polymer was 39.7 g. Further, the melting point of the polymer was 88.4 ° C., and the intrinsic viscosity [η] was 1.60 dl / g. Table 3 shows the measured physical properties of the obtained polymer.

<Production Comparative Example 3 (synthesis of PBR-C3)>
Polymerization was carried out in the same manner as in Production Comparative Example 2, except that 842 ml of hexane and 95 g of 1-butene were charged. The obtained polymer was 15.1 g. The melting point of the polymer was 69.5 ° C., and the intrinsic viscosity [η] was 1.95 dl / g. Table 3 shows the measured physical properties of the obtained polymer.

  With respect to Production Comparative Example 3 having substantially the same melting point as Production Example 3, the ½ crystallization time at 45 ° C. was determined by DSC.

[Example 1]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 100 parts by weight of the propylene-based elastomer PBR-1 obtained by the method of Production Example 1 and Shellsol TG as an organic solvent Was heated to 130 ° C. while purging with nitrogen. Then, 45 parts by weight of methyl methacrylate, 20 parts by weight of isobutyl methacrylate, 14 parts by weight of ethyl acrylate, 15 parts by weight of FM-3, 5 parts by weight of hydroxyethyl methacrylate, methacrylic acid as polymerizable monomers A mixed solution of 1 part by weight and 1 part by weight of di-tert-butyl peroxide (hereinafter abbreviated as PBD) as a polymerization initiator was fed over 4 hours. The temperature was raised to 135 ° C. 30 minutes after the end of feeding, and 0.5 part by weight of PBD was added 30 minutes later. Further, after 1 hour, 50 parts by weight of Shellsol TG and 0.5 parts by weight of PBD were added. 16 hours after this PBD addition
The temperature was raised to 0 ° C., 6 parts by weight of PBD was added, 2 parts by weight was added after 1 hour, and 2 parts by weight were further added after 1 hour. After the addition of PBD, the reaction was allowed to stand for 2 hours to obtain an organic solvent dispersion.

  Shellsol TG used above is an isoparaifin organic solvent manufactured by Shell Japan Co., Ltd., and Plaxel FM-3 used as a polymerizable monomer is an unsaturated fatty acid manufactured by Daicel Chemical Industries, Ltd. Hydroxyalkyl ether modified epsilon-caprolactone.

[Example 2]
Except that the solvent during production was all changed to methylcyclohexane, the temperature in the system was changed to 97 ° C. in all steps, and the polymerization initiator was changed to tert-butylperoxy-2-ethylhexanoate (hereinafter abbreviated as PBO). An organic solvent dispersion was obtained in the same manner as in Example 1.

[Example 3]
140 parts by weight of PBR-1 initially charged, 300 parts by weight of Shellsol TG, and 27 parts by weight of methyl methacrylate, 12 parts by weight of isobutyl methacrylate, and 8.4 parts by weight of ethyl acrylate are fed over 4 hours. , 9 parts by weight of FM-3, 3 parts by weight of hydroxyethyl methacrylate, 0.6 parts by weight of methacrylic acid, 0.6 parts by weight of PBD, and 0 PBD added at 1 hour and 2 hours after the end of feeding An organic solvent dispersion was obtained in the same manner as in Example 1 except that the amount was changed to 3 parts by weight.

[Example 4]
60 parts by weight of PBR-1 initially charged, 200 parts by weight of Shellsol TG, and 63 parts by weight of methyl methacrylate, 28 parts by weight of isobutyl methacrylate, and 19.6 parts by weight of ethyl acrylate are fed over 4 hours. , 21 parts by weight of FM-3, 7 parts by weight of hydroxyethyl methacrylate, 1.4 parts by weight of methacrylic acid, 1.4 parts by weight of PBD, 0 PBD added at 1 hour and 2 hours after the end of feeding An organic solvent dispersion was obtained in the same manner as in Example 1 except that the amount of Shellsol TG to be added was changed to 100 parts by weight to 0.7 parts by weight.

[Example 5]
The mixed liquid fed over 4 hours is changed to 45 parts by weight of methyl methacrylate, 10 parts by weight of isobutyl methacrylate, 29 parts by weight of ethyl acrylate, 15 parts by weight of hydroxyethyl methacrylate, 1 part by weight of methacrylic acid, and 1 part by weight of PBD. Except that, an organic solvent dispersion was obtained in the same manner as in Example 1.

[Example 6]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 100 parts by weight of the propylene-based elastomer PBR-1 obtained by the method of Production Example 1 and Shellsol TG as an organic solvent Was heated to 130 ° C. while purging with nitrogen. Next, the dropping resin solution obtained by the following method was dropped into this over 1 hour. After the dropping, the system was heated to 140 ° C. and 6 parts by weight of PBD was added. After 1 hour, 2 parts by weight was added, and after 1 hour, 2 parts by weight were added and reacted. After the addition of PBD, the reaction was allowed to stand for 2 hours to obtain an organic solvent dispersion.

(Drip resin solution)
Into a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 70 parts by weight of xylene and 30 parts by weight of anone were charged, and heated to 100 ° C. while replacing with nitrogen. Next, 45 parts by weight of methyl methacrylate, 14 parts by weight of ethyl acrylate, 20 parts by weight of isobutyl methacrylate, 5 parts by weight of hydroxyethyl acrylate, 15 parts by weight of FM-3, 1 part by weight of methacrylic acid and 1 part by weight of PBO are contained therein. Part of the mixture was fed over 4 hours. The temperature was raised to 110 ° C. 30 minutes after the end of feeding, and 0.5 part by weight of PBO was added 30 minutes later. One more hour after the addition of PBO, 0.5 part by weight of PBO was added and allowed to react for 2 hours after the addition of PBO to obtain a resin solution.

[Example 7]
An organic solvent dispersion was obtained in the same manner as in Example 3 except that all the solvents during production were changed to methylcyclohexane, the temperature in the system was changed to 97 ° C. in all steps, and the polymerization initiator was changed to PBO.

[Example 8]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 100 parts by weight of propylene elastomer PBR-1 obtained by the method of Production Example 1 and 150 parts by weight of Shellsol TG The temperature was raised to 130 ° C. while charging and replacing with nitrogen. Next, 3 parts by weight of Plaxel FM-3 and 4 parts of styrene were added and dispersed therein as a polymerizable monomer having a functional group, and then 3 parts by weight of PBD was added and reacted for 2 hours. Thereafter, 115 parts by weight of Shellsol TG was added to obtain a resin in which a part of the thermoplastic elastomer was modified with a functional group. Next, while maintaining the inside of the reactor at 130 ° C., 45 parts by weight of methyl methacrylate, 14 parts by weight of ethyl acrylate, 20 parts by weight of isobutyl methacrylate, 5 parts by weight of 2-hydroxyethyl methacrylate and plaxel were used as polymerizable monomers. A mixed solution of 15 parts by weight of FM-3, 1 part by weight of methacrylic acid and 1 part by weight of PBD was fed over 4 hours. 30 minutes after the end of feeding, the temperature was raised to 135 ° C., and after 30 minutes, 50 parts by weight of Shellsol TG was added, 0.5 part by weight of PBD was added, and 0.5 part by weight of PBD was further added after 1 hour. did. 30 minutes after the addition of PBD, the temperature was raised to 160 ° C., and the mixture was further left to react for 1 hour to obtain an organic solvent dispersion.

[Example 9]
An organic solvent dispersion was obtained in the same manner as in Example 5, except that all the solvents at the time of production were changed to methylcyclohexane, the temperature in the system was changed to 97 ° C. in all steps, and the polymerization initiator was changed to PBO.

[Example 10]
An organic solvent dispersion was obtained in the same manner as in Example 1 except that PBR charged in the initial stage was changed to PBR-2.

[Example 11]
An organic solvent dispersion was obtained in the same manner as in Example 2 except that PBR charged in the initial stage was changed to PBR-2.

[Example 12]
An organic solvent dispersion was obtained in the same manner as in Example 3 except that PBR charged in the initial stage was changed to PBR-2.

[Example 13]
An organic solvent dispersion was obtained in the same manner as in Example 4 except that the initial PBR charged was changed to PBR-2.

[Example 14]
An organic solvent dispersion was obtained in the same manner as in Example 5 except that PBR charged in the initial stage was changed to PBR-2.

[Example 15]
An organic solvent dispersion was obtained in the same manner as in Example 6 except that PBR charged in the initial stage was changed to PBR-2.

[Example 16]
An organic solvent dispersion was obtained in the same manner as in Example 7 except that PBR charged in the initial stage was changed to PBR-2.

[Example 17]
An organic solvent dispersion was obtained in the same manner as in Example 8 except that PBR charged in the initial stage was changed to PBR-2.

[Example 18]
An organic solvent dispersion was obtained in the same manner as in Example 9 except that PBR charged in the initial stage was changed to PBR-2.

[Example 19]
An organic solvent dispersion was obtained in the same manner as in Example 1 except that the initial PBR charged was changed to PBR-3.

[Example 20]
An organic solvent dispersion was obtained in the same manner as in Example 2 except that PBR charged in the initial stage was changed to PBR-3.

[Example 21]
An organic solvent dispersion was obtained in the same manner as in Example 3 except that the PBR charged initially was changed to PBR-3.

[Example 22]
An organic solvent dispersion was obtained in the same manner as in Example 4 except that the initial PBR charged was changed to PBR-3.

[Example 23]
An organic solvent dispersion was obtained in the same manner as in Example 5 except that PBR charged in the initial stage was changed to PBR-3.

[Example 24]
An organic solvent dispersion was obtained in the same manner as in Example 6 except that PBR charged in the initial stage was changed to PBR-3.

[Example 25]
An organic solvent dispersion was obtained in the same manner as in Example 7 except that PBR charged in the initial stage was changed to PBR-3.

[Example 26]
An organic solvent dispersion was obtained in the same manner as in Example 8, except that PBR charged in the initial stage was changed to PBR-3.

[Example 27]
An organic solvent dispersion was obtained in the same manner as in Example 9, except that PBR charged in the initial stage was changed to PBR-3.

[Examples 28 to 41]
In each of the organic solvent dispersions obtained in Examples 1 to 11, 14, 15, and 17, D-177HN (manufactured by Mitsui Takeda Chemical Co., Ltd., product name) was used as a curing agent, respectively, OH / NCO = 0.95. To obtain an organic solvent dispersion.

[Examples 42 to 55]
To each organic solvent dispersion obtained in Examples 1 to 11, 14, 15, and 17, titanium oxide pigment (Tipeque-CR93 (trade name, manufactured by Ishihara Sangyo Co., Ltd.)) was added to each resin component (the organic solvent). The organic solvent dispersed in the organic solvent dispersion 100 was added in an amount of 30% by weight to the dispersion (excluding the organic solvent) and mixed in a ratio (weight ratio) of xylene / toluene / methyl isobutyl ketone = 1/1/1. A coating resin was obtained by adding 40 parts by weight per part by weight.

[Comparative Example 1]
An organic solvent dispersion was obtained in the same manner as in Example 1 except that PBR charged in the initial stage was changed to PBR-C1.

[Comparative Example 2]
An organic solvent dispersion was obtained in the same manner as in Example 6 except that PBR charged in the initial stage was changed to PBR-C1.

[Comparative Example 3]
An organic solvent dispersion was obtained in the same manner as in Example 8, except that PBR charged in the initial stage was changed to PBR-C1.

[Comparative Example 4]
An organic solvent dispersion was obtained in the same manner as in Example 1 except that PBR charged in the initial stage was changed to PBR-C2.

[Comparative Example 5]
An organic solvent dispersion was obtained in the same manner as in Example 6 except that PBR charged in the initial stage was changed to PBR-C2.

[Comparative Example 6]
An organic solvent dispersion was obtained in the same manner as in Example 8, except that PBR charged in the initial stage was changed to PBR-C2.

[Comparative Example 7]
An organic solvent dispersion was obtained in the same manner as in Example 1 except that PBR charged in the initial stage was changed to PBR-C3.

[Comparative Example 8]
An organic solvent dispersion was obtained in the same manner as in Example 6 except that PBR charged in the initial stage was changed to PBR-C3.

[Comparative Example 9]
An organic solvent dispersion was obtained in the same manner as in Example 8, except that PBR charged in the initial stage was changed to PBR-C3.

<Evaluation and results>
((1. Stability of organic solvent dispersion))
The organic solvent dispersions obtained in Examples 1 to 27 and Comparative Examples 1 to 9 were allowed to stand for 1 month under the respective conditions of nonvolatile content of 40% and room temperature of 5 ° C, or nonvolatile content of 40% and room temperature of 40 ° C. The state of the dispersion was evaluated. After the lapse of one month, the dispersion was not confirmed to be separated and precipitated, and the viscosity was not increased, and the separation and precipitation were not confirmed but the viscosity was changed to Δ, separated and / or The observation of precipitation was evaluated as x. The results of Examples 1 to 27 are shown in Tables 4-1 to 4-2, and the results of Comparative Examples 1 to 9 are shown in Table 5.

((2. Sprayability of organic solvent dispersion))
Using a paint gun (Wider spray gun (product name; W-88-13H5G) manufactured by Iwata Co., Ltd.), atomizing pressure of 4 kg / cm ² , opening of the nozzle one rotation, temperature in the paint booth 30
Spray the organic solvent dispersions obtained in Examples 1 to 41 and Comparative Examples 1 to 9 and the coating resins obtained in Examples 42 to 55 at 0 ° C. and observe whether stringing occurs. And what was not generated was evaluated as ○, and even one was evaluated as ×. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

((3. Physical property evaluation method))
(1) Test on polypropylene (hereinafter also referred to as PP) plate (PP plate test piece-1)
The organic solvent dispersions obtained in Examples 1 to 41 and Comparative Examples 1 to 9 and the coating resins obtained in Examples 42 to 55 were made of polypropylene whose surface was wiped with isopropyl alcohol (manufactured by Prime Polymer Co., Ltd., product) After being applied to a square plate of name: X708) so that the film thickness after drying was 10 μm, it was placed in an oven at 80 ° C. for 30 minutes.

(1) -1. Tack test Gauze was placed on the coating surface at room temperature, and a load of 1 kg / cm ² was applied to the obtained coating film, and the presence or absence of hair remaining on the coating film when gauze was removed was evaluated. The case where no hair remained in the coating film was evaluated as ◯, and the case where hair remained was evaluated as x. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

(1) -2. Cross-cut peel test A test piece with a cross cut was prepared from the obtained coating film according to the cross-cut peel test method described in JIS-K-5400, and an adhesive cellophane tape (cello tape (registered trademark)) was prepared. ) (Manufactured by Nichiban Co., Ltd.) was applied to the grid, and then immediately pulled in a 90 ° direction to peel off, and the number of grids that did not peel was evaluated among 100 grids. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

(PP plate test piece-2)
After coating the white topcoat paint on the coating film obtained with the test piece -1 of the PP plate so that the film thickness after drying becomes 100 μm, and forming the coating film and leaving it to stand at room temperature for 10 minutes. Then, it was baked for 30 minutes in an oven at 100 ° C.

  In addition, the white top coat used above is OLESTAR Q186 (trade name; manufactured by Mitsui Chemicals, Inc., non-volatile content 50%, hydroxyl value 30 mg KOH / g) 100 g, Tipeque-CR93 (trade name; Ishihara Sangyo ( Co., Ltd.) and OLESTAR NM89-50G (trade name; Mitsui Chemicals, non-volatile content 50%, NCO content 6%), which is a curing agent having an isocyanate group, is OH. A mixture of /NCO=0.95 (molar ratio) was used.

(1) -3. Cross-cut peel test The obtained coating film was evaluated by performing a cross-cut peel test described in (1) -2. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

(1) -4. Peel strength test Peel strength is measured by making a cut with a width of 1 cm in the coating film, peeling off the end, measuring the peel strength at 180 ° direction at a speed of 50 mm / min, and measuring the peel strength. Evaluations were made with ◯ for 1200 g / cm or more, Δ for 800 g / cm or more and less than 1200 g / cm, and x for less than 800 g / cm. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

(PP plate test piece-2: weather resistance test)
The PP plate test piece-2 was evaluated according to a sunshine carbon arc lamp type for 1000 hours in accordance with the accelerated weathering test method described in JIS-K-5400.

(1) -5. Gloss retention after the weather resistance test From the 60-degree specular gloss before and after the test (JIS-K-5400), the measured value retention (%) = (gloss after test / initial gloss) × 100 The evaluation was evaluated as ○ when the gloss retention was 80% or more and no discoloration was observed, Δ when 60% or more and less than 80%, and × when less than 60%. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

(1) -6. Cross-cut peel test after weather resistance test The obtained coating film was evaluated by performing a cross-cut peel test described in (1) -2. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

(PP plate test piece-2: water resistance test)
The PP plate test piece-2 was evaluated by immersing it in warm water adjusted to 40 ° C. for 240 hours.

(1) -7. Appearance after water resistance test The coating film after the test was evaluated for the presence or absence of bulges, etc., and those having no change were marked with ◯ and those with a change in the paint film such as bulge were marked with ×. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

(1) -8. Cross-cut peel test after water resistance test The obtained coating film was evaluated by performing the cross-cut peel test described in (1) -2. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

(Test piece of PP film and aluminum foil-1)
The organic solvent dispersions obtained in Examples 1 to 55 and Comparative Examples 1 to 9 were each applied to an aluminum foil so that the film thickness after drying was 3 μm, and then placed in an oven at 100 ° C. for 10 minutes. did. On this coating film, the PP film was heat-sealed by applying a pressure of 0.098 MPa at 100 ° C. for 1 second by a method based on JISZ1707.

(2) -1. Peel strength test The obtained test piece was cut into a 1.5 cm strip shape, and the end portion was measured in a 180 ° direction at a speed of 50 mm / min, and the peel strength was measured. The evaluation was evaluated as Δ for 1000 g / cm or more and less than 2000 g / cm, and x for less than 1000 g / cm. The results of Examples 1 to 55 are shown in Tables 4-1 to 4-3, and the results of Comparative Examples 1 to 9 are shown in Table 5.

Claims (17)

A propylene / 1-butene random copolymer (A);
alpha, polymer of at least one copolymerizable monomer selected from the group consisting of monomers and other copolymerizable monomer having a β- monoethylenically unsaturated group (B) and (C) A composite resin produced by generating radicals and reacting , and an organic solvent dispersion of a composite resin comprising an organic solvent,
The propylene / 1-butene random copolymer (A) is
(1) containing units derived from propylene in an amount of 60 to 90 mol% and units derived from 1-butene in an amount of 10 to 40 mol%;
(2) The triad isotacticity obtained from ¹³ C-NMR spectrum measurement is 85% or more and 97.5% or less,
(3) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is in the range of 1 to 3,
(4) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1-12 dl / g,
(5) The melting point (Tm) measured by a differential scanning calorimeter is in the range of 40 to 120 ° C.,
(6) The relationship between the melting point (Tm) and the 1-butene constituent unit content M (mol%) is
146 exp (−0.022 M) ≧ Tm ≧ 125 exp (−0.032 M)
And
The copolymerizable monomer (B) is at least one copolymer selected from the group consisting of (meth) acrylic acid esters, aromatic vinyl compounds, vinyl acetate, vinyl propionate, and α-olefins having 2 to 20 carbon atoms. An organic solvent dispersion of a composite resin comprising a functional monomer (B-1). The propylene / 1-butene random copolymer (A) and the polymer (C) are in a weight ratio of (A) / (C) = 10/90 to 90/10. Organic solvent dispersion of composite resin.   The coating material containing the organic solvent dispersion of the composite resin of Claim 1 or 2.   The primer containing the organic solvent dispersion of the composite resin of Claim 1 or 2.   An adhesive containing the organic resin dispersion of the composite resin according to claim 1.   The additive containing the organic solvent dispersion of the composite resin of Claim 1 or 2.   The binder containing the organic solvent dispersion of the composite resin of Claim 1 or 2.   A film obtained from the organic solvent dispersion of the composite resin according to claim 1.   The organic solvent dispersion of the composite resin according to claim 1 or 2, wherein the copolymerizable monomer (B) contains a copolymerizable monomer having active hydrogen and / or a hydroxyl group.   A paint containing the organic resin dispersion of the composite resin according to claim 9 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.   The primer containing the organic solvent dispersion of the composite resin of Claim 9, and the hardening | curing agent which can react with active hydrogen and / or a hydroxyl group.   An adhesive containing the organic resin dispersion of the composite resin according to claim 9 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group. The additive containing the organic solvent dispersion of the composite resin of Claim 9, and the hardening | curing agent which can react with active hydrogen and / or a hydroxyl group.   The binder containing the organic solvent dispersion of the composite resin of Claim 9, and the hardening | curing agent which can react with active hydrogen and / or a hydroxyl group. The film containing the organic solvent dispersion of the composite resin of Claim 9, and the hardening | curing agent which can react with active hydrogen and / or a hydroxyl group.   The coating film formed by apply | coating the coating material, primer, adhesive agent, additive, or binder in any one of Claims 3-7.   The coating film formed by apply | coating the coating material, primer, adhesive agent, additive, or binder in any one of Claims 10-14.