JP2009114314A - Resin composition, coating material containing the same, coating film, and process for forming coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that forms coating films exhibiting excellent adhesion to various moldings etc. and that is excellent in storage stability at low temperature. <P>SOLUTION: The resin composition is provided by mixing a photopolymerization initiator (d) in a resin solution (a) containing a modified product of a propylene-1-butene copolymer (A) in organic solvent. The propylene-1-butene copolymer (A) includes 50-95 mol% of propylene units and 5-50 mol% of 1-butene units and has a molecular weight distribution in the range of 1-3 as measured by GPC and a limiting viscosity of 0.1-12 dl/g. The modified product of the propylene-1-butene copolymer (A) is obtained by polymerizing a particular copolymerizable monomer (C) in the presence of a propylene-1-butene copolymer (A) in organic solvent at a weight ratio of (A)/(C)=1/9 to 9/1 to provide a resin mixture, followed by further carrying out polymerization reaction by generating radical. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition obtained by mixing a photopolymerization initiator in a resin solution containing a modified product of a specific propylene / 1-butene copolymer. More specifically, the present invention relates to a resin composition useful as a paint, primer, adhesive, or the like suitable for application to a polyolefin resin film, sheet, foam, or molded product.

  Polyolefin-based resins generally have high productivity and excellent moldability, and have many advantages such as light weight, rust prevention, impact resistance, etc. Widely used as furniture, miscellaneous goods, building materials, etc. Polyolefin resins are generally non-polar and crystalline, unlike polar resins such as polyurethane resins, polyamide resins, acrylic resins, and polyester resins. It is very difficult to apply or adhere to a polyolefin resin molded product using an adhesive or an adhesive.

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

  However, in the painting and adhesion using general-purpose paints and adhesives known in the past, not only a large equipment cost is required, but also a long time is required for implementation, and the finish is not uniform. This was the cause of the difference in surface treatment.

Therefore, as a coating composition for improving the above-described problems, a resin composition obtained by mixing a photopolymerization initiator in a resin solution containing a modified thermoplastic resin has been proposed (for example, see Patent Document 1). ). Specific examples of the thermoplastic resin include polyolefins and styrene-based thermoplastic elastomers. Although this resin composition was a resin having excellent adhesion strength, further improvements in storage stability at low temperatures, tackiness of the coating film during film formation, and adhesion were desired.
International Publication No. 02/057357 Pamphlet

  The present invention has been made in view of the problems of the prior art, and can form a coating film exhibiting excellent adhesion to an untreated polyolefin resin film, sheet, foam, or molded article. An object of the present invention is to provide a resin composition that is capable of being excellent in storage stability at a low temperature and having little tackiness of a coating film during film formation.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the following resin composition is excellent in storage stability at a low temperature, and completed the present invention.
That is, the resin composition of the present invention is
A resin composition obtained by mixing a photopolymerization initiator (d) with a resin solution (a) containing a modified product of propylene / 1-butene copolymer (A) in an organic solvent,
The propylene / 1-butene copolymer (A) is
(1) A unit derived from propylene is contained in an amount of 50 to 95 mol% and a unit derived from 1-butene is contained in an amount of 5 to 50 mol% (provided that all the structural units are 100 mol%),
(2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1 to 3,
(3) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1-12 dl / g,
Monomer having a modified product of the propylene / 1-butene copolymer (A) having an α, β-monoethylenically unsaturated group in the presence of the propylene / 1-butene copolymer (A) in an organic solvent. Or a copolymerizable monomer (C) composed of the monomer and other copolymerizable monomers at a weight ratio of (A) / (C) = 1/9 to 9/1. It is a modified product obtained by further generating a radical and carrying out a polymerization reaction.

  It is preferable that the resin composition of the present invention further contains at least one selected from the group consisting of fats and oils, derivatives of fats and oils, epoxy resins and polyester resins as the third component.

At least one of the third components preferably has a polymerizable unsaturated bond in the molecule.
The polymerization reaction is preferably performed in the presence of an organic peroxide.

The organic peroxide is preferably an organic oxide having a tert-butyl group and / or a benzyl group.
The resin composition of the present invention may be a resin composition obtained by removing the organic solvent contained in the resin composition and diluting with an arbitrary organic solvent.

It is preferable that at least a part of the copolymerizable monomer (C) is a monomer having active hydrogen and / or a hydroxyl group.
The present invention includes a method for forming a coating film characterized by applying the resin composition and then irradiating with light.

The present invention includes a coating film obtained by the above method.
The present invention includes a coating material containing a main agent containing the resin composition and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.

The present invention includes a method for forming a coating film characterized in that the coating material is applied and then irradiated with light to be cured.
The present invention includes a coating film obtained by the above method.

  The resin composition of the present invention can form a coating film exhibiting excellent adhesion to an untreated polyolefin resin film, sheet, foam, or molded product, and has low storage stability at low temperatures. Excellent and less tack on the coating during film formation.

Next, the present invention will be specifically described.
The resin composition according to the present invention is obtained by mixing a photopolymerization initiator (d) with a resin solution (a) containing a modified product of a propylene / 1-butene copolymer (A) in an organic solvent. The propylene / 1-butene copolymer (A) is (1) a unit derived from propylene in an amount of 50 to 95 mol%, and a unit derived from 1-butene is 5 to 50 mol%. (2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1-3, 3
) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1 to 12 dl / g, and the modified product of the propylene / 1-butene copolymer (A) is a propylene / 1-butene copolymer in an organic solvent. In the presence of the polymer (A), a monomer having an α, β-monoethylenically unsaturated group, or a copolymerizable monomer (C) comprising the monomer and other copolymerizable monomers, (A) / (C) = 1/9 to 9/1 polymerized to obtain a resin mixture, which is a modified product obtained by further generating radicals and causing a polymerization reaction. To do. The resin composition of the present invention is excellent in storage stability at a low temperature by using the specific propylene / 1-butene random copolymer (A).

(Propylene / 1-butene copolymer (A))
The propylene / 1-butene copolymer (A) (PBR) used in the present invention satisfies the following (1) to (3), preferably satisfies (4) to (6), and more preferably (7). (8) is satisfied.

  In the propylene / 1-butene copolymer (A) used in the present invention, (1) units derived from propylene are 50 to 95 mol%, preferably 50 to 90 mol%, more preferably 55 to 85 mol%, Preferably, the unit derived from 1-butene is 5 to 50 mol%, preferably 10 to 50 mol%, more preferably 15 to 45 mol% in an amount of 60 to 85 mol%, particularly preferably 65 to 80 mol%. More preferably, it contains an amount of 15 to 40 mol%, particularly preferably 20 to 35 mol% (provided that all the structural units are 100 mol%).

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

  The propylene / 1-butene copolymer (A) used in the present invention has a molecular weight distribution (Mw / Mn) determined by (2) gel permeation chromatography (GPC) in the range of 1 to 3, preferably 1. More preferably, it is 1.9 to 2.5.

  The propylene / 1-butene copolymer (A) used in the present invention has (3) intrinsic viscosity measured in decalin at 135 ° C. of 0.1 to 12 dl / g, preferably from 0.5 to 10 dl / g. Preferably it is 1-5 dl / g.

The propylene / 1-butene copolymer (A) used in the present invention preferably has a triad isotacticity (mm fraction) determined from (4) ¹³ C-NMR spectrum measurement of 85% or more and 97.5% or less. , Preferably 87% to 97%, more preferably 90% to 97%. By giving the specific mm fraction, the melting point can be lowered with a relatively high propylene content, which is preferable.

The triad isotacticity (mm fraction) is an index indicating the stereoregularity of the propylene / 1-butene copolymer (PBR), 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 copolymer (PBR) is determined from the ¹³ C-NMR spectrum, it is specifically assumed that (i) head-tail as three chains including propylene units present in the polymer chain. The mm fraction is measured for 3 linked propylene units and (ii) propylene units / butene units 3 linked consisting of head-to-tail bonded propylene units and butene units, the second unit being a propylene unit. .

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 propylene / 1-butene copolymer (PBR) is completely obtained in hexachlorobutadiene containing a small amount of deuterated benzene using propylene / 1-butene copolymer (PBR) as a lock solvent in a sample tube. And then dissolved at 120 ° C. by a proton complete decoupling method. 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 copolymer (PBR) measured in this way, 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). .

  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 copolymer (PBR) is (i) a head-to-tail coupled propylene unit or (ii) a head-to-tail coupled propylene unit. 3 chain of propylene / butene consisting of a butene unit and containing a propylene unit in the second unit, and a ¹³ C-NMR spectrum (hexachlorobutadiene solution) for the side chain methyl group of the propylene unit of the second unit in the third chain 21.0-21.9 ppm (first region) when the total area of the peak appearing in 19.5-21.9 ppm (methyl carbon region) is taken as 100%. As a percentage (percentage) of the area of the peak appearing in the following formula (1),

  As described above, the propylene / 1-butene copolymer (A) (PBR) used in the present invention preferably has a mm fraction of 85% or more and 97.5% or less, more preferably 87%. It is 97% or less, More preferably, it is 90% or more and 97% or less. By providing the specific mm fraction, the melting point can be lowered with a relatively high propylene content. The propylene / 1-butene copolymer (PBR) has the following structures (iii), (iv) and (v) in addition to the above-described three-chain (i) and (ii) bonded to the head. It has a small amount of a partial structure containing a regioregular unit as shown, and the peak derived from the side chain methyl group of the propylene unit due to such other bonds is also the 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 copolymer (A) used in the present invention has (5) a melting point (Tm) measured by a differential scanning calorimeter of preferably 40 to 120 ° C., more preferably 50 to 100 ° C., further Preferably it is 55-90 degreeC.

In the propylene / 1-butene copolymer (A) used in the present invention, (6) The relationship between the melting point (Tm) and the 1-butene structural unit content M (mol%) is preferably 146 exp (−0.022 M ) ≧ Tm ≧ 125exp (−0.032M)
More 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 copolymer (A) used in the present invention is preferably (7) a crystallization rate measured at 45 ° C. of the propylene / 1-butene copolymer (1 / 2 crystallization time) is 10 minutes or less, more preferably 7 minutes or less.

  The propylene / 1-butene 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 copolymer (PBR) is 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. .
Further, the propylene / 1-butene copolymer (A) (PBR) used in the present invention is a heterogeneous bond unit (position irregularity) based on 2,1-insertion or 1,3-insertion of propylene present in a propylene chain. It may have a small amount of structure containing (unit).

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 an area such as Iαβ directly from the spectrum due to overlapping peaks, it can be corrected with a carbon peak having a corresponding area.
The propylene / 1-butene copolymer (A) (PBR) used in the present invention has different propylene constituents based on the 2,1-insertion of propylene present in the propylene chain obtained as described above. It may be contained in the unit at a rate 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 in the propylene / 1-butene copolymer (PBR) can be obtained from the βγ peak (resonance at around 27.4 ppm).

The propylene / 1-butene 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 copolymer (A) (PBR) used in the present invention as described above can be produced, for example, by the method described in WO 2004/088775.

(Modified product of propylene / 1-butene copolymer (A))
The modified product of the propylene / 1-butene copolymer (A) contained in the resin solution (a) used in the present invention is α, in the presence of the propylene / 1-butene copolymer (A) in an organic solvent. A monomer having a β-monoethylenically unsaturated group, or a copolymerizable monomer (C) comprising the monomer and another copolymerizable monomer is represented by (A) / (C) = 1/9 A resin composition, which is a modified product obtained by polymerizing at a weight ratio of ˜9 / 1 to obtain a resin mixture and then further generating radicals to cause a polymerization reaction.

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, and isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate,
(Meth) acrylic such as tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. Acid esters;
Hydroxyl-containing vinyls such as hydroxyethyl acrylate and 2-hydroxyethyl (meth) acrylate;
Carboxyl group-containing vinyls such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, and monoesterified products thereof;
Aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene;
Other examples include acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide, methacrylamide, methylol acrylamide, methylol methacrylamide, ethylene, propylene, and α-olefins having 4 to 20 carbon atoms.

Descriptions such as methyl (meth) acrylate described herein indicate methyl acrylate or methyl methacrylate.
Other copolymerizable monomers include, for example, monomers having an α, β-monoethylenically unsaturated group, such as carboxylic anhydrides such as maleic anhydride, phthalic anhydride, and succinic anhydride. Examples thereof include a copolymerizable monomer.

Examples of the organic solvent to be used include aromatic hydrocarbons such as xylene, toluene, and ethylbenzene;
Aliphatic hydrocarbons such as hexane, heptane, octane, decane;
Cycloaliphatic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane;
Aliphatic alcohols such as ethanol and isopropyl alcohol;
Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone;
Ester solvents such as butyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoacetate;
Examples include ether solvents such as dipropyl ether, propylene glycol monomethyl ether, and diethylene glycol dibutyl ether. Moreover, the organic solvent to be used may be a mixture of two or more of these. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferably used. Among the aliphatic hydrocarbons, aliphatic hydrocarbons having 6 to 20 carbon atoms and alicyclic hydrocarbons are particularly preferable.

The organic solvent is usually used in such an amount that the nonvolatile content when the propylene / 1-butene copolymer (A) is dissolved in the organic solvent is in the range of 2 to 70% by mass.
Examples of the polymerization initiator that can be used for polymerizing the copolymerizable monomer (C) in the presence of the propylene / 1-butene copolymer (A) include, for example, di-tert-butyl peroxide, tert-butyl peroxide. Organic peroxides such as oxy-2-ethylhexanoate, benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide;
Examples include azo compounds such as azobisisobutyronitrile, 4,4′-azobis (4-cyanopentanoic acid), and 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propioamide). You may use these individually or in mixture of 2 or more types.

  The polymerization initiator is usually in the range of 0.01 to 15 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the copolymerizable monomer (C). Used in

  Copolymerizability comprising a monomer having an α, β-monoethylenically unsaturated group, or the monomer and other copolymerizable monomers in the presence of the propylene / 1-butene copolymer (A) As a specific example of the method for polymerizing the monomer (C), for example, the propylene / 1-butene copolymer (A) is dissolved in the organic solvent described above, and the copolymerizable monomer (C) and the polymerization initiator described above are dissolved. The propylene / 1-butene copolymer (A) / copolymerizable monomer (C) is fed at a weight ratio of 1/9 to 9/1, more preferably 2/8 to 8/2. The method of polymerizing can be mentioned. The resin mixture thus obtained can be further polymerized by generating radicals to obtain a resin solution (a) containing a modified product of the propylene / 1-butene copolymer (A). Since the resin composition using the resin solution (a) containing the modified product of the propylene / 1-butene copolymer (A) obtained by this method has excellent stability and low viscosity, High concentration painting is possible.

  As a method for generating the radical, 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 benzoyl, benzoin methyl ether, benzoin isopropyl ether, benzyl, benzophenone, 2-hydroxy-2-methylpropiophenone, 2,2-diethoxyacetophenone, benzylmethyl ketal, anthraquinone, chloranthraquinone. , Ethyl anthraquinone, butyl anthraquinone, diphenyl sulfide, dithiocarbamate, 2-chlorothioxanthone, α-chloromethylnaphthalene, anthracene, 3,3 ′, 4,4′-tetrabenzophenone, 2,4,6-trimethylbenzoyl diphenylphos Examples include fin oxide. You may use these individually or in mixture of 2 or more types.

Further, these photopolymerization initiators may be used in combination with amines such as Michler's ketone, trimethylamine, and alkylmorpholine.
The said photoinitiator is 0.01-10 mass parts normally with respect to 100 mass parts of total amounts of the said propylene / 1-butene copolymer (A) and a copolymerizable monomer (C), More preferably It is used in the range of 0.1 to 5 parts by mass.

Organic peroxides include di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, dioctyl having a tert-butyl group and / or a benzyl group in the molecule. Milperoxide, tert-butylperoxybenzoate, cumene hydroperoxide and the like can be mentioned. You may use these individually or in mixture of 2 or more types.

Of the above-mentioned organic peroxides, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate are more preferably used. That is, an organic peroxide having a tert-butyl group and / or a benzyl group in the molecule has a relatively high hydrogen abstraction capability, and is composed of a propylene / 1-butene copolymer (A) and a copolymerizable monomer (C). There is an effect of improving the graft ratio with the polymer, and by using these, the resulting resin composition is extremely difficult to cause a separation phenomenon.

  The organic peroxide is usually 2 to 50 parts by mass, more preferably 3 to 30 parts per 100 parts by mass of the total amount of the propylene / 1-butene copolymer (A) and the copolymerizable monomer (C). It can be used in the range of parts by mass. It is preferable to add the organic peroxide in small amounts as much as possible. That is, although it depends on the amount of the organic peroxide used, it is preferable to add it little by little over time or continuously.

(Resin solution (a))
The resin solution used in the present invention is a resin solution (a) containing a modified product of the propylene / 1-butene copolymer (A) in an organic solvent. The organic solvent used for the resin solution (a) is usually the same organic solvent as used for obtaining the modified product of the propylene / 1-butene copolymer (A). Moreover, after obtaining the modified product of the propylene / 1-butene copolymer (A), the solvent may be removed and the modified product of the propylene / 1-butene copolymer (A) may be added to another organic solvent.

(Photopolymerization initiator (d))
As the photopolymerization initiator (d) used in the present invention, any photopolymerization initiator (d) may be used as long as it generates radicals upon irradiation with ultraviolet rays. For example, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzyl, benzophenone, 2-hydroxy-2-methylpropiophenone, 2,2-diethoxyacetophenone, benzyldimethylketanol,
Anthraquinone, chloroanthraquinone, ethylanthraquinone, butylanthraquinone, diphenylsulfide, dithiocarbamate, 2-chlorothioxanthone, α-chloromethylnaphthaleneanthracene, 3,3,4,4-tetrabenzophenone, 2,4,6-trimethylbenzoyldiphenyl Examples include phosphine oxide. These can be used alone or in combination of two or more.

These photopolymerization initiators may be used in combination with amines such as Michler's ketone, trimethylamine, and alkylmorpholine.
Among the photopolymerization initiators described above, benzophenone, 3,3,4,4-tetrabenzophenone, etc. have a relatively high hydrogen abstraction ability, and have an effect of improving the adhesion with the base material. What has is used more suitably.

  If the amount of the photopolymerization initiator used is too small, the adhesion strength with the substrate tends to be reduced, and if the amount used is too large, molecular breakage and the like are likely to occur. In view of the tendency to reduce the adhesion strength of the resin, it is usually used in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin composition.

(Production method of resin composition)
The resin composition according to the present invention can be produced by mixing and stirring the above-described resin solution (a) and photopolymerization initiator (d) by a known method.

In the step of producing the resin composition according to the present invention, a third component can be added to the resin composition according to the present invention.
For example, in the step of polymerizing the copolymerizable monomer (C) in the presence of the propylene / 1-butene copolymer (A), the step of generating a radical and then performing the polymerization reaction, etc. And at least one selected from the group consisting of fats and oils, epoxy resins and polyester resins can be added within a range not impairing the object of the present invention.

Examples of the fats and oils used as the third component include linseed oil, soybean oil, castor oil, and purified products thereof.
Examples of the fats and oils used as the third component are short oils obtained by modifying a polybasic acid such as phthalic anhydride and a polyhydric alcohol such as glycerin, pentaerythritol, and ethylene glycol with a fat (fatty acid). Alkyd resin, medium oil alkyd resin, long oil alkyd resin, etc., or rosin modified alkyd resin modified with natural resin, synthetic resin and polymerizable monomer, phenol modified alkyd resin, epoxy modified alkyd resin, acrylated alkyd resin, urethane Examples thereof include modified alkyd resins.

  Moreover, the fats and oils which have a polymerizable unsaturated bond obtained by adding the carboxylic anhydride which has a polymerizable unsaturated bond in a molecule | numerator to the fats and oils which have a hydroxyl group can also be used. Two or more of the above oils and fats and their derivatives can be used in combination.

  Examples of the epoxy resin used as the third component include an epoxy resin obtained by glycidyl etherification of bisphenol A, bisphenol F, novolac, etc., an epoxy resin obtained by adding propylene oxide or ethylene oxide to bisphenol A, and the like. Can be mentioned. Moreover, you may use the amine modified epoxy resin etc. which added the polyfunctional amine to the epoxy group. Furthermore, an aliphatic epoxy resin, an alicyclic epoxy resin, a polyether type epoxy resin, etc. are also mentioned.

  In addition, epoxy resins having a polymerizable unsaturated bond in the molecule obtained by adding a carboxylic anhydride having a polymerizable unsaturated bond in the molecule to the epoxy resin having a hydroxyl group can also be used. Two or more of the above epoxy resins can be used in combination.

The polyester resin used as the third component is obtained by condensation polymerization of a carboxylic acid component and an alcohol component. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic anhydride, naphthalene dicarboxylic acid, and succinic acid. , Glutaric acid, adipic acid, azelaic acid, 1,10-decanedicarboxylic acid, cyclohexanedicarboxylic acid, polyvalent carboxylic acids such as trimellitic acid, maleic acid, fumaric acid, and lower alcohol esters thereof, hydroxycarboxylic acids such as paraoxybenzoic acid, etc. Acids and monovalent carboxylic acids such as benzoic acid can be used. These can be used in combination of two or more.

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, Neopentylglycol, Trimethylolethane, Trimethylolpropane, Glycerin, Pentaerythritol, Ethylene oxide adduct of bisphenol A, Propylene oxide adduct of bisphenol A, Ethylene oxide adduct of hydrogenated bisphenol A, Hydrogenated bisphenol A propylene oxide adduct of A or the like can be used. Two or more of these can be used in combination.

  Moreover, the polyester resin which has 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 polyester resin can be used alone or in combination of two or more.

  The above-mentioned third component can be added while being fed into the reactor, or can be initially charged into the reactor for use. Moreover, a 3rd component is 0.5-60 mass parts normally with respect to 100 mass parts of resin components of a resin solution (a), Preferably it is used in the ratio of 5-40 mass parts.

Further, the third component may be added after the step of generating and reacting radicals.
In particular, a resin composition using oils and fats and derivatives of oils and fats as the third component has particularly good stability, good compatibility with other resins, and markedly improved peel strength. In particular, those containing castor oil are highly effective.

  Moreover, the resin composition obtained in this way can be substituted with an arbitrary organic solvent by a known method. As an organic solvent which can be substituted, the organic solvent etc. which are used for the resin solution (a) containing the modified product of a propylene / 1-butene copolymer (A) in an organic solvent can be used.

The resin composition according to the present invention thus obtained can be used as a paint, a primer or an adhesive.
Among the resin compositions according to the present invention, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, as at least a part of the copolymerizable monomer (C),
A resin composition using a monomer having active hydrogen and / or a hydroxyl group such as acrylic acid or methacrylic acid can be used as a coating in combination with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group. For example, by mixing with 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 having a urethane bond, a primer, and an adhesive. .

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 diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate;
Aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate;
Examples thereof include polyisocyanate compounds such as alicyclic diisocyanates such as isophorone diisocyanate and dicyclohexylmethane diisocyanate. Also obtained by adding polypropylene oxide and / or ethylene oxide to one or more of these polyisocyanate compounds, polyhydric alcohols such as trimethylolpropane and triethanolamine, and initiators such as trimethylolpropane. Terminal isocyanate adducts obtained by reaction with polyether polyols or polyester polyols can also be used.

An amino resin composed of melamine, urea or the like can also be used as a curing agent.
The resin composition according to the present invention and the curing agent capable of reacting with active hydrogen and / or hydroxyl group can be used in any ratio.

  The blending ratio when the curing agent capable of reacting with active hydrogen and / or hydroxyl group is a curing agent having an isocyanate group is the activity contained in the modified product of the propylene / 1-butene copolymer (A) according to the present invention. Hydrogen and the isocyanate group contained in the curing agent preferably have an equivalent ratio in the range of 0.5: 1.0 to 1.0: 0.5, and 0.8: 1.0 to 1. More preferably, it is in the range of 0: 0.8.

  Further, when the curing agent capable of reacting with active hydrogen and / or hydroxyl group is an amino resin, the mass ratio of the resin composition / amino resin solid according to the present invention is used in the range of 95/5 to 20/80. Is preferable, and the range of 90/10 to 60/40 is more preferable.

Moreover, a monofunctional (meth) acrylate and urethane acrylate can be mixed and used for the resin composition of this invention by a well-known method.
Monofunctional (meth) acrylates include 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, phenoxy (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di And cyclopentenyloxyethyl (meth) acrylate. These may be used alone or in combination of two or more.

  The urethane (meth) acrylate is a urethane (meth) acrylate selected from aromatic, aliphatic and cycloaliphatic urethane (meth) acrylates, and includes one or more isocyanate groups and one or more polymerizable ( It is a polymerizable urethane (meth) acrylate composed of a (meth) acryl group. The urethane (meth) acrylate may be a polyurethane (meth) acrylate selected from aromatic, aliphatic and cycloaliphatic polyurethane (meth) acrylates. These may be used alone or in combination of two or more. These urethane (meth) acrylates and polyurethane (meth) acrylates are reaction products of terminal isocyanate groups and hydroxyl group-containing (meth) acrylates, and these reaction products can be produced by known methods. it can.

  The resin composition according to the present invention obtained as described above can be used as a paint, a primer, an adhesive, and the like, and further, if necessary, an antioxidant, a weather resistance stabilizer, and a heat resistance inhibitor. In the range which does not impair the objective of this invention, components, such as various stabilizers, such as an additive, can be contained.

  The resin composition according to the present invention or the resin composition according to the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is applied to the surface of a film, sheet, foam, molded article or the like. The method is not particularly limited, but it is preferable to carry out the method by spray coating. For example, it can be applied by spraying onto the surface of a film, sheet, foam or molded article with a spray gun. Application can usually be easily performed at room temperature, and it is preferable to irradiate ultraviolet rays after application.

Here, the method of irradiating the coating film with ultraviolet rays is not particularly limited, and the ultraviolet rays are radiated with such an intensity that the article to be coated is not deformed or discolored.
The film thickness is preferably in the range of 0.1 to 50 μm after drying, and more preferably in the range of 0.5 to 30 μm.

Moreover, it does not specifically limit about a drying method, It can dry by appropriate methods, such as natural drying and heat forced drying.
In addition, the coating composition obtained by mixing the resin composition according to the present invention or the curing agent capable of reacting with active hydrogen and / or a hydroxyl group into the resin composition according to the present invention has a primer in addition to the use as the coating composition. For example, it is possible to apply other paints to the surface after drying as described above by electrostatic coating, spray coating, brush coating, or the like.

  Other paints used are not particularly limited, and include solvent-type thermoplastic acrylic resin paints, solvent-type thermosetting acrylic resin paints, acrylic-modified alkyd resin paints, epoxy resin paints, polyurethane resin paints, and melamine resin paints. be able to.

  The coating composition in which the resin composition according to the present invention or the resin composition according to the present invention is mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is, for example, a polyolefin such as polyethylene or polypropylene, or an ethylene-propylene copolymer. Polymers, ethylene-butene copolymers, propylene-butene copolymers, films, sheets, foams or molded articles made of olefin copolymers such as ethylene-propylene-butene copolymers, and polypropylene and synthetic rubber It can be suitably used as a top coating material for films, sheets, foams or molded articles comprising the following, and can also be used for surface treatment of polyamide resins, unsaturated polyester resins, polycarbonate resins and the like.

The resin composition according to the present invention or the resin composition according to the present invention contains active hydrogen and / or
Alternatively, a paint mixed with a curing agent capable of reacting with a hydroxyl group is also useful as a primer for paints or adhesives mainly composed of polyurethane resin, polyester resin, melamine resin, epoxy resin, and the like. It can be used to improve the adhesion of a paint or the like to the surface of an object and to form a coating film that is more excellent in sharpness.

  In particular, the resin composition according to the present invention, or the paint obtained by mixing the resin composition according to the present invention with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is a film, sheet, foam, or It can be suitably used as a top coating material for molded articles, films made of polypropylene and synthetic rubber, sheets, foams, molded articles, molded articles using unsaturated polyester, epoxy resins, polyurethane resins, and the like.

  Furthermore, the coating composition obtained by mixing the resin composition according to the present invention or a curing agent capable of reacting with active hydrogen and / or a hydroxyl group into the resin composition according to the present invention is the surface of these films, sheets, foams, or molded articles. It can also be suitably used as a primer for improving the adhesion of the paint to the surface.

〔Example〕
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. 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)
The 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, usually at a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, Measurement was performed under the measurement conditions of a spectral width of 1500 Hz, a filter width of 1500 Hz, a pulse repetition time of 4.2 sec, and an integration number of 2000 to 5000. From this spectrum, P ₁ , P ₂ , P ₁₂ (P ₁ is an ethylene content fraction, P ₂ was calculated by determining the 1-butene content fraction, and P ₁₂ was the ratio of (ethylene)-(1-butene) chain in all the bimolecular chains.

(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 measured physical properties of the obtained polymer are shown in Table 2. [Production Example 4 (synthesis of PBR-4)]
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. 1 mmol of aluminum,
And 0.005 mmol of a titanium catalyst supported on magnesium chloride in terms of Ti atoms, and propylene was continuously supplied to carry out polymerization for 30 minutes while maintaining the total pressure at 0.7 MPa. A similar post-polymerization treatment 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 2 shows the measured physical properties of the obtained polymer.

[Production Example 5 (synthesis of PBR-5)]
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 2 shows the measured physical properties of the obtained polymer.

[Production Example 6 (synthesis of PBR-6)]
Polymerization was carried out in the same manner as in Production Example 5 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 2 shows the measured physical properties of the obtained polymer.

  For Production Example 6 having substantially the same melting point as Production Example 3, the ½ crystallization time at 45 ° C. was determined by DSC.

[Production Examples 7 to 18 (Production of resin solution containing modified polyolefin)]
In the (co) polymer (B) solution or the acid anhydride (co) polymer (B) solution obtained in the following production examples, PBR and a solvent described in the column of reaction in Table 3, and the production examples 10 to 11 In Table 3, the third component described in Table 3 was added, and the temperature was raised to 135 ° C. while purging with nitrogen. In addition, when the solvent was toluene, it heated up to 105 degreeC. Subsequently, di-tert-butyl peroxide (hereinafter abbreviated as PBD), which is an organic peroxide in an amount described in the reaction column of Table 3, was added thereto. In addition, when the solvent was toluene, PBO was added. This organic peroxide was added in the amount shown in Table 3 by first adding 3/7 of the amount, 2/7 after 1 hour, and 2/7 after that. To be added, it was added in a total of three times and allowed to react. After reacting for 2 hours after the addition of the organic peroxide, the dilution solvent described in the reaction column of the above table was added and diluted to a non-volatile content of 30% to obtain a resin solution containing the modified polyolefin. .

(Production of (co) polymer (B) for Production Examples 7 to 17)
A four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube was charged with the solvent described in the column for the synthesis of the (co) polymer (B) in Table 3 and 100 ° C. with nitrogen substitution. The temperature was raised to Then, in this, t-butylperoxy- which is a polymerization initiator described in the copolymerizable monomer (C) and polymerization initiator 1 described in the column of synthesis of (co) polymer (B) in Table 3 A mixed solution of 2-ethylhexanoate (hereinafter abbreviated as PBO) is fed over 4 hours, and after 1 hour has elapsed from the end of the feed, PBO described in the polymerization initiator 2 is added, and further reacted for 2 hours. I let you. Thereafter, the dilution solvent described in the column of the synthesis of the (co) polymer (B) in the above table was added and diluted to a non-volatile content of 50% to produce a (co) polymer (B).

(Production of (co) polymer (B) to which carboxylic anhydride for Production Example 18 was added)
A four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube was charged with the solvent described in the column for the synthesis of the (co) polymer (B) shown in Table 3 and replaced with nitrogen. The temperature was raised to ° C. Next, the mixture of the copolymerizable monomer (C) described in the column for the synthesis of the (co) polymer (B) shown in Table 3 and the PBO described in the polymerization initiator 1 is fed over 4 hours. After 1 hour from the end of the feed, PBO described in Polymerization Initiator 2 was added and left for another 2 hours. Then, the dilution solvent described in the column of the synthesis of the (co) polymer (B) in the above table was added, and diluted until the nonvolatile content was 50%. Then, the temperature was set to 100 ° C., and the acid anhydride in the table was added and reacted for 1 hour to produce a (co) polymer (B) to which acid anhydride was added.

  In addition, the numerical value of each component in Table 3 indicates parts by weight.

[Production Examples 19 to 39 (Production of resin solution containing modified polyolefin)]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with PBR and a solvent shown in Tables 4 and 5, and heated to 130 ° C. while purging nitrogen. In addition,
When the solvent was Isopar E, the temperature was raised to 110 ° C. Here, a mixture of the copolymerizable monomer (C) and the polymerization initiator shown in Tables 4 and 5 and the third component shown in Table 4 in Production Examples 22 to 27 was fed over 4 hours. 1 hour after the end of the feed, the indicated amount of the diluted solvent 1 was added, and the indicated amount of the polymerization initiator PBD was added. In addition, when there is no description of the numerical value in the dilution solvent 1, a solvent is not added. 30 minutes after the addition of the polymerization initiator, the temperature was raised to 160 ° C., and 30 minutes later, 3/7 of the organic peroxide PBD shown in Tables 4 and 5 was added. / 7, and then, after 1 hour, the remaining 2/7 was added in three portions and reacted. In addition, when the solvent was Isopar E, PBO was used as a polymerization initiator at 110 ° C. Thereafter, the reaction was allowed to stand for 2 hours, and the dilution solvent 2 shown in Table 3 was added to dilute to a non-volatile content of 40% to obtain a resin solution containing a modified polyolefin.

  The olestar C1000 (trade name; manufactured by Mitsui Chemicals, Inc., oil-based polyol, non-volatile content 100%, hydroxyl value 160 mgKOH / g) used in the third component is an oil and fat, Epomic R140 (trade name; Mitsui Chemicals). Co., Ltd., non-volatile content 100%, epoxy equivalent 190 g / eq) is an epoxy resin, Almatex P646 (trade name; made by Mitsui Chemicals, non-volatile content 60%, hydroxyl value 35 mg KOH / g) is polyester. Shellsol 70 (trade name) used above is an isoparaffin-based organic solvent manufactured by Shell Japan.

  In addition, Olester C1000 modified resin is obtained by adding 1.4 parts of maleic anhydride to 100 parts of Olester C1000, adding maleic anhydride by stirring at 100 ° C. for 3 hours, and polymerizable unsaturated in the molecule. It contains a bond.

  Epoxy R140-modified resin is prepared by adding 1.2 parts of maleic anhydride to 100 parts of epomic R140 and adding maleic anhydride by stirring at 100 ° C. for 3 hours to contain a polymerizable unsaturated bond in the molecule. It is a thing.

  ALMATEX P646 modified resin is 100 parts of ALMATEX P646 with 0.04 part of maleic anhydride added and stirred at 100 ° C for 3 hours to add maleic anhydride to form polymerizable unsaturated bonds in the molecule. It is contained.

  In addition, the numerical value of each component in Tables 4 and 5 indicates parts by weight.

[Production Examples 40 to 49 (Production of resin solution containing modified polyolefin)]
Resin solution in the same production method as Production Examples 4 to 6, 9 to 11, and 18 to 20, except that PBR was changed to Best Plast 750 (Degussa Japan Co., Ltd., Mw / Mn = 5, Mw = 90000). Got.

The Examples and Comparative Examples described below were performed, and the results are shown in Tables 6 to 11.
[Examples 1 to 33]
To the resin solutions obtained in the above Production Examples 7 to 39, Irgacure 500 (trade name; manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) is used as a photopolymerization initiator (d). And a benzophenone eutectic mixture) were added to obtain a resin composition.

The addition amount was such that Irgacure 500 was 2 parts by weight per 100 parts by weight of the resin component in the resin solution.
[Examples 34 to 66]
In the resin solutions obtained in the above Production Examples 7 to 39, Aronix M400 (made by Toagosei Co., Ltd., pentafunctional monomer) as a reactive monomer was dissolved in MIBK at 40%, and Irgacure 500. The resin composition was obtained by mixing.

  In addition, the addition amount is 20 parts by weight of the monomer resin component and 2 parts by weight of Irgacure 500, which is obtained by dissolving 40% of Aronix M400 in MIBK per 100 parts by weight of the resin component in the resin solution. did.

[Examples 67 to 76]
Takenate D-178N (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., HDI allophanate) was added to the resin solutions obtained in Production Examples 7 to 9, 12, 19 to 21, and 28 to 30 by OH / NCO 1/1 ( The resin composition was obtained by mixing Aronics M400 in MIBK at 40% and Irgacure 500.

  The amount of addition is 100% by weight of the resin component in the resin solution, each of which is mixed with Takenate D-178N so as to be 1/1 (molar ratio) with OH / NCO, and Aronix M400 is added to MIBK at 40%. 20 parts by weight of dissolved material and 2 parts by weight of Irgacure 500 were added.

[Comparative Examples 1 to 10]
2 parts by weight of Irgacure 500 was added to the resin solutions obtained in Production Examples 40 to 49, respectively, with respect to 100 parts by weight of the resin component in the resin solution to obtain a resin composition.

[Comparative Examples 11 to 20]
In the resin solutions obtained in the above Production Examples 40 to 49, Aronix M400 dissolved in MIBK at 40% and Irgacure 500 were each 20 weights per 100 parts by weight of the resin component in the resin solution. Part and 2 parts by weight were mixed to obtain a resin composition.

[Comparative Examples 21 to 30]
Takenate D-178N was mixed with the resin solutions obtained in the above Production Examples 40 to 49 so that the molar ratio was 1/1 with OH / NCO, and Aronix M400 was dissolved in MIBK at 40%. And Irgacure 500 were mixed so as to be 20 parts by weight and 2 parts by weight with respect to 100 parts by weight of the resin component in the resin solution, respectively, to obtain a resin composition.

[Evaluation and results]
<Stability of resin composition>
The resin compositions obtained in Examples 1 to 66 and Comparative Examples 1 to 20 were allowed to stand for 2 weeks under the respective conditions of a nonvolatile content of 40%, room temperature and 40 ° C., and the state of the solution was evaluated. After two weeks, this aqueous solution showed neither separation nor precipitation confirmed and thickened, ◎, neither separation nor precipitation confirmed, but viscosity changed, ○, separated and / or precipitated. Of those observed that were easily dispersible by stirring, and those that were not easily dispersible by stirring where separation and / or precipitation were observed were evaluated as x.

<Sprayability of aqueous resin composition>
Using a coating gun (Wider spray gun manufactured by Iwata Coating Machine Co., Ltd. (trade name: W-88-13H5G)), the atomizing pressure is 4 kg / cm ² , the nozzle is rotated once, and the temperature in the coating booth is 30 ° C. Then, spray the aqueous resin composition solutions obtained in each of the examples and comparative examples, and observe whether stringing occurs or not. evaluated.

<Method for evaluating physical properties>
(1) Test with PP plate (Test piece-1 of PP plate)
After applying the resin composition obtained above onto a square plate made of polypropylene (product name: X708, manufactured by Prime Polymer Co., Ltd.) whose surface is wiped with isopropyl alcohol so that the film thickness after drying is 10 μm. And placed in an oven at 80 ° C. for 30 minutes. Next, using an ultraviolet irradiation device (manufactured by Nippon Batteries Co., Ltd., EPSH-600-3S type) in which one 80 W / cm high-pressure mercury lamp is installed perpendicular to the passing direction, the conveyor speed is set at a position 15 cm below the light source. It was moved at a speed of 10 m / min and irradiated with ultraviolet rays.

(1) -1. Tack test A 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 the 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.

(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. ) (Product of Nichiban Co., Ltd.)) was pasted on the grid, and it was quickly pulled and peeled in the direction of 90 °, and the number of grids that did not peel was evaluated among 100 grids.

(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; 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.
(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. 1200g /
Evaluation was made with ◎ for cm or more, ◯ for 1000 g / cm or more and less than 1200 g / cm, Δ for 800 g / cm or more and less than 1000 g / cm, and × for less than 800 g / cm.

(1) -5. Appearance after water resistance test The specimen was immersed in water adjusted to 40 ° C. for 240 hours, and then the appearance of the coating film was evaluated.
(1) -6. Cross-cut peel test after water resistance test The cross-cut peel test described in (1) -2 was evaluated for the coating film after the test piece was immersed in water adjusted to 40 ° C. for 240 hours.

(2) Test with ethylene sheet <Sheet specimen-1>
The resin composition obtained above was adjusted so that the non-volatile content would be 20% by adding the same solvent used in the production of the resin solution. Next, Tuffmer A-4085 (trade name; manufactured by Mitsui Chemicals, Inc., MFR (ASTM D 1238, 190 ° C., 2.16 kg load) 3.6 g / 10 min, density (ASTM D 1505), which is a polyolefin-based resin The sheet prepared at 0.88 g / cm 3) was wiped with isopropyl alcohol, and the resin composition was applied with a brush so that the film thickness after drying was 2 μm and dried at room temperature. Next, using an ultraviolet irradiation device (manufactured by Nippon Batteries Co., Ltd., EPSH-600-3S type) in which one 80 W / cm high-pressure mercury lamp is installed perpendicular to the passing direction, the conveyor speed is set at a position 15 cm below the light source. It was moved at a speed of 10 m / min and irradiated with ultraviolet rays.

(2) -1. Cross-cut peel test The obtained coating film was evaluated by performing a cross-cut peel test described in (1) -2.
(2) -2. Follow-up test After the sheet was bent at 90 °, the film was returned to its original state, and a coating film appearance of the bent portion and a cross-cut peel test were performed. The case where the appearance was good and peeling did not occur at the bent portion was evaluated as “◯”, the case where the coating film floated at the bent portion was evaluated as Δ, and the case where peeling occurred at the time of bending was evaluated as “X”.

<Sheet Specimen-2>
Further, a white top coat was applied to the coating obtained in Preparation-1 of the sheet so that the film thickness after drying was 20 μm to form a coating, left at room temperature for 10 minutes, and then 100 ° C. The peel strength of the coating film that had been baked for 30 minutes in the oven was measured.

(2) -3. 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. The evaluation was evaluated as ◎ for those having 1200 g / cm or more, ◯ for those having 1000 g / cm or more and less than 1200 g / cm, Δ for those having 800 g / cm or more but less than 1000 g / cm, and × for those having 800 g / cm or less.

(3) Test with foam base material <Foam test piece>
The resin composition obtained above was added with the same solvent as used at the time of producing the resin solution to adjust the nonvolatile content to 10%. Subsequently, the foam obtained by the method described in Example 1 of JP-A-2000-344924 was immersed in a mixed solvent (methylcyclohexane / isopropyl alcohol / methyl ethyl ketone = 65 parts / 20 parts / 15 parts) for 1 minute. Thereafter, the resin composition was applied with a brush so that the film thickness after drying was 1 μm and dried. Next, using an ultraviolet irradiation device (manufactured by Nippon Batteries Co., Ltd., EPSH-600-3S type) in which one 80 W / cm high-pressure mercury lamp is installed perpendicular to the passing direction, the conveyor speed is set at a position 15 cm below the light source. It was moved at a speed of 10 m / min and irradiated with ultraviolet rays. About the coating film after irradiating said ultraviolet-ray, the peeling strength test was done by the following two methods.

(3) -1. Peel strength test (Evaluation 1)
An aqueous urethane resin (manufactured by Tosei Chemical Co., Ltd., product name: BOND ACE W-01) was applied onto the coating film after being irradiated with the above ultraviolet rays with a brush so that the film thickness after drying was 5 μm. A primer (manufactured by Tosei Chemical Co., Ltd., product name: D) was dried and a synthetic rubber sheet (trade name: NIPOL BR1220 manufactured by JSR Co., Ltd.) wiped with acetone so that the film thickness after drying was 1 μm. -PLY 007) was applied, and further, an aqueous urethane resin (manufactured by Tosei Chemical Co., Ltd., product name: BOND ACE W-01) was applied with a brush so as to have a film thickness after drying of 5 μm, and dried. The product was pressed with a force of 40 kg / m 2 at 60 ° C. for 10 seconds and left for 48 hours. Next, a 1 cm wide cut was made on the rubber side of what was obtained as described above, and after peeling off the end portion, the end portion was pulled at a speed of 200 mm / min in the direction of 180 ° to measure the peel strength. When the strength was 5 kg / cm or more, ◎, when 4 kg / cm or more and less than 5 kg / cm, ○, when 3 kg / cm or more and less than 4 kg / cm, Δ or less than 3 kg / cm, and x.

(3) -2. Peel strength test (Evaluation 2)
An aqueous urethane resin (manufactured by Tosei Chemical Co., Ltd., product name: BOND ACE W-01) was applied onto the coating film after being irradiated with the above ultraviolet rays with a brush so that the film thickness after drying was 5 μm. Primer (manufactured by Tosei Chemical Co., Ltd., trade name: BOND ACE 232H) so that the film thickness after drying is 1 μm on urethane sheet (Dae Jin Synthesis Chemical, polyurethane sheet for shoes of DRY method) ), And after applying an aqueous urethane resin (manufactured by Tosei Chemical Co., Ltd., product name: BOND ACE W-01) with a brush so that the film thickness after drying is 5 μm. The pressure was applied at 60 ° C. with a force of 40 kg / m 2 for 10 seconds and left for 48 hours. Next, the urethane sheet side obtained as described above was cut with a width of 1 cm, and after peeling off the end portion, the end portion was measured in a 180 ° direction at a speed of 200 mm / min, and the peel strength was measured. When the peel strength was 5 kg / cm or more, ◎, when 4 kg / cm or more and less than 5 kg / cm, ○, when 3 kg / cm or more and less than 4 kg / cm, Δ or less than 3 kg / cm, and x.

Claims (12)

A resin composition obtained by mixing a photopolymerization initiator (d) with a resin solution (a) containing a modified product of a propylene / 1-butene copolymer (A) in an organic solvent,
The propylene / 1-butene copolymer (A) is
(1) A unit derived from propylene is contained in an amount of 50 to 95 mol% and a unit derived from 1-butene is contained in an amount of 5 to 50 mol% (provided that all the structural units are 100 mol%),
(2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1 to 3,
(3) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1-12 dl / g,
Monomer having a modified product of the propylene / 1-butene copolymer (A) having an α, β-monoethylenically unsaturated group in the presence of the propylene / 1-butene copolymer (A) in an organic solvent. Or a copolymerizable monomer (C) composed of the monomer and other copolymerizable monomers at a weight ratio of (A) / (C) = 1/9 to 9/1. A resin composition, which is a modified product obtained by further generating radicals to cause a polymerization reaction.   The resin composition according to claim 1, further comprising at least one selected from the group consisting of fats and oils, fats and oils derivatives, epoxy resins and polyester resins as the third component.   The resin composition according to claim 2, wherein at least one of the third components has a polymerizable unsaturated bond in the molecule.   The resin composition according to claim 1, wherein the polymerization reaction is performed in the presence of an organic peroxide.   The resin composition according to claim 4, wherein the organic peroxide is an organic oxide having a tert-butyl group and / or a benzyl group.   A resin composition obtained by desolvating the organic solvent contained in the resin composition according to any one of claims 1 to 5 and diluting with an arbitrary organic solvent.   The resin composition according to claim 1, wherein at least a part of the copolymerizable monomer (C) is a monomer having active hydrogen and / or a hydroxyl group.   A method for forming a coating film, comprising applying the resin composition according to claim 1 and then irradiating light.   The coating film obtained by the method of Claim 8.   A paint comprising a main agent containing the resin composition according to claim 7 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.   A method for forming a coating film, which comprises applying the coating material according to claim 10 and then curing it by irradiating light.   The coating film obtained by the method of Claim 11.