JP6687279B2 - Resin composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a resin composition, and more particularly to a resin composition containing a modified olefin polymer, which can be suitably used for applications such as pressure-sensitive adhesives and adhesives.

Polyolefins, especially polyethylene and polypropylene, are used in various molded products because they are inexpensive, have high strength, and are easy to handle. However, since polyolefin has a low surface energy and is a poorly adhesive resin having low adhesiveness with an adhesive, various studies have been conducted to improve the adhesiveness to polyolefin.
For example, regarding an acrylic monomer that is often used as a pressure-sensitive adhesive material, a method of controlling the polarity by changing the molecular structure of the monomer is known (see Patent Document 1). Further, there is known a method of improving the adhesion to a polyolefin substrate by dispersing a polyolefin in the form of an aqueous dispersion in a pressure-sensitive adhesive (see Patent Document 2).

JP, 2005-086231, A JP, 2011-046777, A

Since conventional polyolefins have high crystallinity even when modified with maleic anhydride or the like, it is not possible to directly disperse the polyolefin in the acrylic monomer, and the acrylic monomer and the polyolefin are mixed in the form of an aqueous emulsion. . However, in the form of an aqueous emulsion, there are problems that it takes a long time to dry and that a surfactant added to make the dispersed particle size of the polyolefin finer reduces the tackiness. Moreover, when the molecular weight of the polyolefin used is high, the adhesion to the polyolefin substrate becomes poor.
An object of the present invention is to provide a resin composition in which a polyolefin is dispersed in an acrylic monomer even if it is not in the form of an aqueous emulsion.

As a result of intensive studies, the present inventor has found that a resin composition containing a modified olefin polymer having a specific structure and physical properties can be obtained by modifying a modified olefin polymer into an acrylic monomer without forming an aqueous emulsion. It was found that the dispersibility is excellent. The present invention has been completed based on such knowledge.
That is, the present invention provides the following resin composition.

<1> A resin composition containing a modified olefin polymer satisfying the following (1) to (3) as a component (A) and one or more (meth) acryloyl group-containing compounds as a component (B).
(1) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 2.5 dL / g.
(2) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./minute to obtain the highest temperature side of the melting endothermic curve. The melting point (Tm-D) defined as the peak top of the observed peak is not observed or is 0 to 100 ° C.
(3) The half-crystallization time measured by a differential scanning calorimeter (DSC) is 3 minutes or longer, or the crystallization peak measured by a differential scanning calorimeter (DSC) is not observed.
<2> The resin composition according to <1>, wherein the modified olefin polymer satisfies the following (4).
(4) Using a differential scanning calorimeter (DSC), the sample was held in a nitrogen atmosphere at −10 ° C. for 5 minutes and then heated at 10 ° C./minute to obtain a melting endotherm obtained from a melting endotherm curve. The amount of heat (ΔH-D) is 0 to 80 J / g.
<3> The resin composition according to <1> or <2>, wherein the modified olefin polymer satisfies the following (5).
(5) The acid value is 10 to 250 mgKOH / g.
<4> The resin composition according to any one of <1> to <3>, wherein the modified olefin polymer satisfies the following (6).
(6) The mesotriad fraction [mm] is 55 to 90 mol%.
<5> The resin composition according to any one of <1> to <4>, in which the modified olefin polymer satisfies the following (7) and (8).
(7) The mesopentad fraction [mmmm] is 20 to 80 mol%.
(8) [rrrr] / (1- [mmmm]) is 3.0 or less.
<6> Any of the above items <1> to <5>, in which 50 mol% or more of the monomers constituting the modified olefin polymer is at least one selected from the group consisting of a propylene monomer and a 1-butene monomer. The resin composition according to one.
<7> The above <1> to <, wherein the component (A) is 0.1% by mass or more and 50% by mass or less based on 100% by mass of the total amount of the component (A) and the component (B). The resin composition according to any one of 6>.
<8> The resin composition according to any one of <1> to <7>, wherein the (meth) acryloyl group-containing compound is a compound represented by the following general formula (I) or (II).

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom, an alkyl group, a hetero atom-containing group, an aromatic group, or an alkoxy (poly) alkylene oxide group. ]
<9> A reaction product of the resin composition according to any one of <1> to <8>.
<10> An adhesive containing the reaction product according to <9>.
<11> An adhesive containing the reaction product according to <9>.
<12> A sealing material containing the reaction product according to <9>.
<13> An ink composition containing the reaction product according to <9>.

  The resin composition of the present invention contains a modified olefin-based polymer having a specific structure and physical properties, so that the modified olefin-based polymer in the (meth) acryloyl group-containing compound (acrylic-based monomer) is not required to be in the form of an aqueous emulsion. The dispersibility of the polymer is excellent. Therefore, the pressure-sensitive adhesive or adhesive using the resin composition of the present invention has good affinity to polyolefin, and can be expected to improve the pressure-sensitive adhesiveness or adhesiveness to a polyolefin substrate. Further, since it is not necessary to make it in the form of an aqueous emulsion, there is no problem that it takes a long time to dry and that the surfactant lowers the tackiness.

  The resin composition of the present invention is a resin composition containing a modified olefin polymer having a specific structure and physical properties as a component (A) and one or more (meth) acryloyl group-containing compound as a component (B). is there.

(Component (A): modified olefin polymer)
The resin composition of the present invention contains a modified olefin polymer having a specific structure and physical properties as the component (A). The modified olefin polymer used in the present invention satisfies the following (1) to (3).
(1) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 2.5 dL / g.
(2) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./minute to obtain the highest temperature side of the melting endothermic curve. The melting point (Tm-D) defined as the peak top of the observed peak is not observed or is 0 to 100 ° C.
(3) The half-crystallization time measured by a differential scanning calorimeter (DSC) is 3 minutes or longer, or the crystallization peak measured by a differential scanning calorimeter (DSC) is not observed.

  The modified olefin polymer satisfying the above (1) to (3) has low crystallinity, has high compatibility with the (meth) acryloyl group-containing compound, and does not cause phase separation. Therefore, the pressure-sensitive adhesive or adhesive using the resin composition of the present invention has good affinity to polyolefin, and can be expected to improve the pressure-sensitive adhesiveness or adhesiveness to a polyolefin substrate. In addition, since the dispersibility of the modified olefin polymer in the acrylic monomer is excellent even if it is not in the form of an aqueous emulsion, it is not necessary to make it in the form of an aqueous emulsion, so it takes time to dry or the surfactant does not stick to the surface. There is no problem such as deterioration of sex.

The modified olefin polymer used in the present invention is obtained by acid-modifying an olefin polymer with an organic acid as described later.
As the monomer capable of forming the olefin polymer, one or more kinds of monomers selected from ethylene and α-olefin having 3 to 28 carbon atoms are preferable. Examples of the α-olefin having 3 to 28 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1- Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icosene and the like can be mentioned. The α-olefin monomer is preferably an α-olefin having 3 to 24 carbon atoms, more preferably an α-olefin having 3 to 12 carbon atoms, and particularly preferably an α-olefin having 3 or 4 carbon atoms (that is, a propylene monomer, 1 -Butene monomer), C6-C12 alpha-olefins.
50 mol% or more of the α-olefin constitutional unit in the modified olefin polymer is a unit derived from at least one monomer selected from α-olefins having 3 or 4 carbon atoms (that is, propylene monomer, 1-butene monomer). It is preferably at least 65 mol%, more preferably at least 75 mol%, further preferably at least 80 mol%.
The modified olefin polymer used in the present invention may contain an organic acid and a monomer other than α-olefin within a range that does not impair the effects of the present invention.

(1) Intrinsic viscosity [η]
The intrinsic viscosity [η] of the modified olefin polymer measured at 135 ° C. in a tetralin solvent is 0.01 to 2.5 dL / g, preferably 0.10 to 2.0 dL / g, and more preferably It is 0.10 to 1.8 dL / g, more preferably 0.15 to 1.5 dL / g, and further preferably 0.3 to 0.7 dL / g. When the intrinsic viscosity of the modified polyolefin is within the above range, it is possible to prevent unmanageability due to excessive stickiness or deterioration of fluidity.
The intrinsic viscosity [η] is calculated by measuring the reduced viscosity (η _SP / c) with a Ubbelohde viscometer in tetralin at 135 ° C. and using the following equation (Huggins equation).
η _SP / c = [η] + K [η] ² c
η _SP / c (dL / g): reduced viscosity [η] (dL / g): intrinsic viscosity c (g / dL): polymer viscosity K = 0.35 (Huggins constant)

(2) Melting point (Tm-D)
The melting point (Tm-D) of the modified olefin polymer is not observed or is 0 to 100 ° C. from the viewpoint of dispersibility in the (meth) acryloyl group-containing compound. When the melting point is observed, from the same viewpoint, it is preferably 50 to 100 ° C, more preferably 55 to 90 ° C, and further preferably 57 to 80 ° C.
In the present invention, a differential scanning calorimeter (manufactured by Perkin-Elmer Co., Ltd., trade name: “DSC-7”) was used, and 10 mg of the sample was kept at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then 10 ° C./minute. The melting point (Tm-D) is defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at.
The melting point (Tm-D) can be controlled by appropriately adjusting the monomer concentration and reaction pressure.

(3) Semi-crystallization time The semi-crystallization time of the modified olefin polymer measured by a differential scanning calorimeter (DSC) is 3 minutes or more from the viewpoint of slow crystallization rate, or the differential scanning calorific value. Crystallization peak measured by DSC is not observed. It is preferably 10 minutes or longer, more preferably 30 minutes or longer. When the crystallization rate is slow such that the half crystallization time exceeds 60 minutes, a clear crystallization peak may not be observed.
The "semi-crystallization time" in the present invention means that measured by the following measuring method.

<Method of measuring semi-crystallization time>
A differential scanning calorimeter (DSC) (manufactured by Perkin-Elmer Co., Ltd., trade name: "DSC-7") is used and measured by the following method.
(1) Hold 10 mg of the sample at 25 ° C. for 5 minutes, raise the temperature to 220 ° C. at 320 ° C./sec, and hold for 5 minutes. By cooling at 320 ° C./sec to 25 ° C. and holding for 300 minutes, the time change of the calorific value in the isothermal crystallization process is measured.
(2) When the integrated value of the calorific value from the start of the isothermal crystallization to the completion of the crystallization is 100%, the time from the start of the isothermal crystallization until the integrated value of the calorific value reaches 50% is semi-crystallization. Defined as time.

The modified olefin polymer used in the present invention preferably further satisfies at least one of the following (4) to (6) in addition to the above (1) to (3). Further, when the olefin polymer before being modified is a homopolymer, it is preferable that the following (7) and (8) are satisfied.
(4) Using a differential scanning calorimeter (DSC), the sample was held in a nitrogen atmosphere at −10 ° C. for 5 minutes and then heated at 10 ° C./minute to obtain a melting endotherm obtained from a melting endotherm curve. The amount of heat (ΔH-D) is 0 to 80 J / g.
(5) The acid value is 10 to 250 mgKOH / g.
(6) The mesotriad fraction [mm] is 55 to 90 mol%.
(7) The mesopentad fraction [mmmm] is 20 to 80 mol%.
(8) [rrrr] / (1- [mmmm]) is 3.0 or less.

(4) Melting endotherm (ΔH-D)
The melting endotherm (ΔH-D) of the modified olefin polymer is preferably 0 to 80 J / g, more preferably 10 to 70 J / g, further preferably from the viewpoint of dispersibility in the (meth) acryloyl group-containing compound. Is 20 to 60 J / g, more preferably 30 to 50 J / g.
In the present invention, the melting endotherm (ΔH-D) is measured with a differential scanning calorimeter (DSC) by holding the sample in a nitrogen atmosphere at -10 ° C for 5 minutes and then raising the temperature at 10 ° C / minute. The area enclosed by the line containing the peak of the melting endothermic curve obtained by the above and the line connecting the low temperature side where the calorific value does not change and the high temperature side where the calorific value does not change (the base line) is obtained. It is calculated by.

(5) Acid value The acid value of the modified olefin polymer is preferably 10 to 250 mgKOH / g, more preferably 10 to 200 mgKOH / g, from the viewpoint of dispersibility in the (meth) acryloyl group-containing compound. It is preferably 10 to 100 mgKOH / g, more preferably 10 to 70 mgKOH / g.
In the present invention, the acid value is measured according to JIS K2501: 2003.

(6) Mesotriad fraction [mm]
The modified olefin polymer used in the present invention has a mesotriad fraction [mm] of preferably 55 to 90 mol%, more preferably 60 to 88 mol%, and further preferably 65 to 85 mol%. The mesotriad fraction [mm] is a stereoregularity index showing isotacticity. When the mesotriad fraction [mm] is within the range, the crystallinity becomes low without being poor in handleability due to stickiness and the like. Dispersibility in a (meth) acryloyl group-containing compound is improved.

(7) Mesopentad fraction [mmmm]
The mesopentad fraction [mmmm] is an index showing the stereoregularity of the olefin polymer, and the larger the mesopentad fraction [mmmm], the higher the stereoregularity.
When the olefin polymer before modification is a homopolymer, the modified olefin polymer has a mesopentad fraction [mmmm] of preferably 20 to 80 mol%, more preferably 30 to 80 mol%, and further preferably Is 40 to 75 mol%. When the mesopentad fraction [mmmm] is within the range, the crystallinity is low and the dispersibility in the (meth) acryloyl group-containing compound is improved.

(8) [rrrr] / (1- [mmmm])
The value of [rrrr] / (1- [mmmm]) is calculated from the mesopentad fraction [mmmm] and the racemic pentad fraction [rrrr] and is an index showing the uniformity of the regular distribution of the olefin polymer. .
When the olefin-based polymer before being modified is a homopolymer, the value of [rrrr] / (1- [mmmm]) of the modified olefin-based polymer is preferably 3.0 or less, and more preferably It is 0.001 to 2.5, more preferably 0.001 to 2.0, and particularly preferably 0.01 to 1.0. When the value is within the range, low crystalline components close to amorphous are suppressed, and stickiness after crystallization is suppressed.

Here, the mesotriad fraction [mm], the mesopentad fraction [mmmm], and the racemic pentad fraction [rrrr] are proposed in “Macromolecules, 6, 925 (1973)” by A. Zambelli and others. It is measured using ¹³ C-NMR according to the above method. Further, the racemic meso racemic mesopentad fraction [rmrm], the racemic triad fraction [rr], and the mesoracemic triad fraction [mr] described later are also measured by the above-mentioned method.

  When the olefin polymer is a polyolefin whose main component is polypropylene (90% by mass or more of propylene), the mesopentad fraction [mmmm] can be measured by the following method.

Apparatus: JEOL Ltd., JNM-EX400 type ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / mL
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

The method for calculating the mesopentad fraction M is as follows.
M = (m / S) × 100
R = (γ / S) × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7 to 22.5 ppm

When the olefin-based polymer is a polyolefin containing polybutene as a main component (butene 90% by mass or more), a mesotriad fraction [mm], a mesopentad fraction [mmmm], a racemic pentad fraction [rrrr], And the racemic meso-racemic mesopentad fraction [rmrm], meso-mesaracemic racemic pentad fraction [mmrr] and racemic meso-mesoracemic pentad fraction [rmmr] reported by Asakura et al. In “Polymer lymer Journal, 16,717 ( 1984) ", J. "Macromol. Chem. Phys., C29, 201 (1989)" reported by Randall et al. It can be measured according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
That is, the mesopentad fraction in the poly (1-butene) molecule can be determined by measuring the signals of the methylene group and the methine group using ¹³ C nuclear magnetic resonance spectrum.
^{The 13} C nuclear magnetic resonance spectrum can be measured with the above-described apparatus and conditions.

When the olefin polymer is a polyolefin whose main component is α-olefin having 6 to 28 carbon atoms, the mesotriad fraction [mm], the mesopentad fraction [mmmm], and the racemic pentad fraction [rrrr] are measured by the following methods. , And racemic meso-racemic meso pentad fraction [rmrm], meso-meso-racemic racemic pentad fraction [mmrr] and racemic meso-mesa racemic pentad fraction [rmmr] are described by Asakura et al. In “Macromolecules, 24, 2334 (1991)”. The meso fraction, the racemic fraction, and the racemic meso-racemic meso fraction in the pentad unit in the polyolefin molecule measured by the methyl group signal of the ¹³ C-NMR spectrum in accordance with the method proposed in 1. The stereoregularity increases as the mesopentad fraction [mmmm] increases.
^{The 13} C nuclear magnetic resonance spectrum can be measured with the above-described apparatus and conditions.

The modified olefin polymer used in the present invention preferably further satisfies the following.
(9) Racemic meso Racemic meso pentad fraction [rmrm]
The racemic meso racemic mesopentad fraction [rmrm] is an index showing the randomness of the stereoregularity of the olefin polymer, and the larger the value, the more the randomness of the olefin polymer increases.
The modified olefin polymer has a racemic mesoracemic mesopentad fraction [rmrm] of preferably more than 1.0 mol%, more preferably 1.3 mol% or more, and further preferably 1.5 mol% or more. . The upper limit is usually preferably about 10 mol%, more preferably 7 mol%, further preferably 5 mol%, and particularly preferably 4 mol%. When the value is within the range, the randomness is increased, the crystallinity of the modified olefin polymer is lowered, and the dispersibility in the (meth) acryloyl group-containing compound is improved.

(10) Molecular weight distribution (Mw / Mn)
The modified olefin polymer used in the present invention has a molecular weight distribution (Mw / Mn) of preferably 4.0 or less, more preferably 3.5 or less, still more preferably 3.0 or less, still more preferably 2.5 or less. Is. The narrower the molecular weight distribution of the modified olefin polymer is, the more preferable. If the molecular weight distribution is wide, the amount of low molecular weight components or high molecular weight components will increase, and depending on the application, stickiness may occur, or the fluidity may become too high or too low, making it unsuitable for practical use. is there.

  The weight average molecular weight (Mw) of the modified olefin polymer is preferably 3,000 or more, more preferably 5,000 or more, and further preferably 7,000 or more from the viewpoint of mechanical strength and processability. It is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 100,000 or less.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are in terms of polystyrene measured by the following apparatus and conditions, and the molecular weight distribution (Mw / Mn) is the weight average molecular weight (Mw). ) And the number average molecular weight (Mn).
<GPC measuring device>
Column: "TOSO GMHHR-H (S) HT" manufactured by Tosoh Corporation
Detector: RI detection for liquid chromatogram "WATERS 150C" manufactured by Waters Corporation
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL
Injection volume: 160 μL
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

(Method for producing modified olefin polymer)
The modified olefin polymer used in the present invention can be produced by modifying the olefin polymer. The olefin polymer is obtained by polymerizing one or more kinds of monomers selected from ethylene and α-olefins having 3 to 28 carbon atoms. Specific examples of the α-olefin having 3 to 28 carbon atoms are as described above.
The olefin polymer monomer used for producing the modified olefin polymer is preferably an α-olefin having 3 to 24 carbon atoms, more preferably an α-olefin having 3 to 12 carbon atoms, and particularly preferably 3 carbon atoms. Alternatively, it is an α-olefin of 4 (that is, a propylene monomer, a 1-butene monomer) or an α-olefin having 6 to 12 carbon atoms.
In the olefin polymer used for producing the modified olefin polymer, the content of the constituent unit derived from the α-olefin having 3 or 4 carbon atoms (that is, propylene monomer, 1-butene monomer) constitutes the polymer. The total unit is preferably 50 mol% or more, more preferably 65 mol% or more, further preferably 75 mol% or more, and further preferably 80 mol% or more.

  The olefin-based polymer used for producing the modified olefin-based polymer can be produced, for example, by using a metallocene-based catalyst as described in WO2003 / 087172. In particular, it is preferable to use a transition metal compound in which the ligand forms a crosslinked structure via a crosslinkable group, and above all, a transition metal compound in which a crosslinked structure is formed via two crosslinkable groups is used. A metallocene catalyst obtained by combining a cocatalyst is preferable.

To give a concrete example,
(I) General formula (I)

[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. A ligand selected from the group consisting of a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which form a crosslinked structure via A ¹ and A ^2. , Which may be the same or different from each other, X represents a σ-bonding ligand, and when there are a plurality of X's, the plurality of X's may be the same or different and other X, E ¹ , It may be crosslinked with E ² or Y. Y represents a Lewis base, and when there are plural Y's, the plural Y's may be the same or different and may be crosslinked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent cross-linking group that binds two ligands, which is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other. q is an integer of 1 to 5 and represents [(valence of M) -2], and r is an integer of 0 to 3. ]
And (ii) (ii-1) a compound capable of reacting with the transition metal compound of the component (i) or a derivative thereof to form an ionic complex, and (ii-2) an aluminoxane. A polymerization catalyst containing a component selected from

  The transition metal compound of the component (i) is preferably a double-bridged transition metal compound having a ligand of (1,2 ′) (2,1 ′), for example, (1,2′-dimethylsilylene) ( 2,1′-Dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ) -Bisindenyl zirconium dichloride and the like.

  Specific examples of the compound as the component (ii-1) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate and methyl tetraphenylborate (tri- n-butyl) ammonium, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), triethyl tetrakis (pentafluorophenyl) borate Monium, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate Benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Methylanilinium, dimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Trimethylanilinium borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate dimethylanili Aluminum, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, Ferrocenium trakis (pentafluorophenyl) borate, Tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), Decamethylferrocenium tetrakis (pentafluorophenyl) borate, Silver tetrakis (pentafluorophenyl) borate, Trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, hexa Examples thereof include silver fluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

  Examples of the aluminoxane as the component (ii-2) include known chain aluminoxanes and cyclic aluminoxanes, such as methylalumoxane.

  Also, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride, etc. A propylene-based polymer may be produced in combination with the organoaluminum compound of.

The modified olefin polymer used in the present invention can be produced by modifying the above olefin polymer with a radical initiator and an organic acid. An unsaturated carboxylic acid or its derivative can be used as the organic acid used in this modification treatment.
It is also possible to add a polar group to the olefin polymer only by air oxidation without using a radical initiator or an organic acid.

When acid-modifying with an organic acid, coexistence of active hydrogen-free vinylamine and (meth) acrylic acid ester allows these compounds, together with the organic acid, to add or graft to the radicals generated on the polyolefin, and only polar Not only that, the compatibility of the modified olefin-based polymer with the (meth) acryloyl group-containing compound can be increased in terms of structure.
Examples of the (meth) acrylic acid ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate. And so on.

  Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid and the like. Examples of the derivative include acid / water products, esters, amides, imides, metal salts, and the like. Examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, Examples thereof include butyl acrylate, 2-ethylhexyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butyl maleimide, sodium acrylate and sodium methacrylate. Of these, maleic anhydride and acrylic acid are particularly preferable. These may be used alone or in combination of two or more.

  On the other hand, the radical initiator is not particularly limited, and conventionally known radical initiators, for example, various organic peroxides, azobisisobutyronitrile, azo compounds such as azobisisovaleronitrile, and the like are appropriately selected. Of these, organic peroxides are preferred, although they can be selected and used.

  Examples of the organic peroxide include dibenzoyl peroxide, di- (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, didecanoyl peroxide, di (2,4-dichlorobenzoyl). Diacyl peroxides such as peroxides, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, di-t -Butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne- 3, dialky such as α, α′-bis (t-butylperoxy) diisopropylbenzene Peroxyketals such as luperoxides, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxide Alkyl peresters such as oxyoctoate, t-butylperoxypivalate, t-butylperoxy neodecanoate, t-butylperoxybenzoate, di- (2-ethylhexyl) peroxydicarbonate, diisopropylperoxy Peroxycarbonates such as dicarbonate, di-sec-butylperoxydicarbonate and t-butylperoxyisopropylcarbonate may be mentioned. Of these, dialkyl peroxides are preferable. Moreover, these may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific commercially available products of these organic peroxides include, for example, Perhexin 25B, Perbutyl D, Perbutyl C, Perhexa 25B, Perkmill D, Perbutyl P, Perbutyl H, Perhexyl H, Perxmill H, manufactured by NOF CORPORATION. , Perocta H, Perkmill P, Permenter H, Perbutyl SM, Permek N, Peromer AC, Perhexa V, Perhexa 22, Perhexa CD, Pertetra A, Perhexa C, Perhexa 3M, Perhexa HC, Perhexa TMH, Perbutyl IF, Perbutyl Z, Perbutyl A, perhexyl Z, perhexa 25Z, perbutyl E, perbutyl L, perhexa 25MT, perbutyl I, perbutyl 355, perbutyl MA, perhexyl I, perbutyl IB, perbutyl O, perhexyl O, percyclo O, -Hexa 250, per octa O, per butyl PV, per hexyl PV, per butyl ND, per hexyl ND, per cyclo ND, per octa ND, park mill ND, diper ND, perloyl SOP, perloyl OPP, perloyl MBP, perloyl EEP, perloyl IPP, perloyl NPP, perloyl TCP. , Perloyl IB, perloyl SA, perloyl S, perloyl O, perloyl L, perloyl 355, niper BW, niper BMT, niper CS and the like (all are trade names).

  The amount of the organic acid and the radical initiator to be used is not particularly limited and may be appropriately selected depending on the desired physical properties of the target modified olefin polymer, with respect to 100 parts by mass of the olefin polymer used. The organic acid is usually used in the range of 0.1 to 50 parts by mass, preferably 0.1 to 30 parts by mass, while the radical initiator is usually 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass. Used in the range of.

  The modification method with an organic acid is not particularly limited, but for example, a propylene-based polymer and the above-described organic acid and radical initiator are used at 120 to 300 ° C., preferably using a roll mill, a Banbury mixer, an extruder or the like. Can be modified at a temperature of about 140 to 250 ° C. for 0.01 to 0.5 hours and reacted to modify the olefin polymer to produce a modified olefin polymer. Alternatively, in a hydrocarbon solvent such as butane, pentane, hexane, cyclohexane, or toluene, a halogenated hydrocarbon solvent such as chlorobenzene, dichlorobenzene, or trichlorobenzene, or an appropriate organic solvent such as liquefied α-olefin, or nothing. To produce a modified olefin polymer by modifying the olefin polymer by reacting it at a temperature of about -50 to 300 ° C., preferably about 40 to 180 ° C. for 0.1 to 2 hours under the condition of a solvent. You can

Further, in the present invention, in order to improve the efficiency of the organic acid modification, it can be carried out in the presence of styrene or α-methylstyrene styrene compound. Moreover, the usage-amount is 0.1-10 mass parts normally with respect to 100 mass parts of olefin polymers, Preferably it is the range of 0.1-5 mass parts.
Styrene and α-methylstyrene-based compounds have higher reactivity with radicals than organic acids, so they easily react with the radicals generated on the polyolefin, and by reacting with the organic acid, the polyolefin and the organic acid are efficiently reacted. It becomes possible to react with.

  The amount of acid modification (the amount of modification with an organic acid) is preferably 0.1 to 50% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 10% by mass. When the amount of acid modification is within the range, compatibility with the (meth) acryloyl group-containing compound can be improved.

  The content of the component (A) in the resin composition of the present invention is preferably 0.1 mass% or more, more preferably 100 mass% of the total amount of the component (A) and the component (B). Is 0.5% by mass or more, more preferably 1% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less. When the resin composition of the present invention is used as a pressure-sensitive adhesive, if the content of the component (A) in the resin composition of the present invention is too low, the affinity for polyolefin, which is a difficult-to-adhesive material, becomes insufficient, If it is too large, the tackiness will decrease.

(Component (B): (meth) acryloyl group-containing compound)
The resin composition of the present invention contains at least one (meth) acryloyl group-containing compound as the component (B). In addition, in this specification, "(meth) acryloyl" means "acryloyl" or "methacryloyl". The (meth) acryloyl group-containing compound used in the present invention is not particularly limited as long as it is a compound containing a (meth) acryloyl group, but is preferably represented by the following general formula (I), (II) or (III). Compounds represented by the following general formula (I) or (II) are more preferred.

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom, an alkyl group, a hetero atom-containing group, an aromatic group, or an alkoxy (poly) alkylene oxide group. ]

In the general formulas (I) to (III), R ¹ represents a hydrogen atom or a methyl group. When R ¹ represents a hydrogen atom, the compound represented by any of the general formulas (I) to (III) is an acryloyl group-containing compound. When R ¹ represents a methyl group, the compound represented by any of the general formulas (I) to (III) is a methacryloyl group-containing compound.

In the general formulas (I) to (III), R ² represents a hydrogen atom, an alkyl group, a hetero atom-containing group, an aromatic group, or an alkoxy (poly) alkylene oxide group. In the general formulas (II) and (III), a plurality of R ^{2 s} may be the same as or different from each other.

  The alkyl group is preferably an alkyl group having 1 to 24 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Group, isobutyl group, t-butyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, isooctyl group, decyl group, isodecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, isooctadecyl group, isobornyl Group, eicosyl group and the like. The structure of the alkyl chain may have any of a linear structure, a branched structure and an alicyclic structure.

  Examples of the hetero atom-containing group include groups in which carbon atoms and hydrogen atoms of an alkyl group are substituted with hetero atoms such as oxygen atom, nitrogen atom and silicon atom. Specific examples include glycidyl group, epoxy group, epoxycyclohexylmethyl group, methylglycidyl group, 4-hydroxybutylglycidyl ether group, 4-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxymethyl group. -Cyclohexylmethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 6-hydroxyhexyl group, 8-hydroxyoctyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-tri Methoxysilylpropyl group, 3-triethoxysilylpropyl group, 3-tripropoxysilylpropyl group, 3-tributoxysilylpropyl group, 3-methyldimethoxysilylpropyl group, 3-methyldiethoxysilylpropyl group, 4-dimethyl- 2-one-move Group, monomethylaminoethyl group, dimethylaminoethyl group, monoethylaminoethyl group, diethylaminoethyl group, monomethylaminopropyl group, dimethylaminopropyl group, monoethylaminopropyl group, diethylaminopropyl group, isocyanate methyl group, 2-isocyanate Examples thereof include an ethyl group.

  The aromatic group is preferably an aromatic group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a phenoxyethyl group and a benzyl group.

  Specific examples of the alkoxy (poly) alkylene oxide group include a methoxy polyethylene glycol group, an ethoxy polyethylene glycol group, a methoxy polypropylene glycol group, an ethoxy polypropylene glycol group and the like.

  The (meth) acryloyl group-containing compound is preferably at least one selected from the group consisting of 2-ethylhexyl acrylate and acrylamide.

(Other ingredients)
The resin composition of the present invention may contain components other than the above-mentioned components (A) and (B) within a range that does not impair the effects of the present invention.

  The resin composition of the present invention may be dissolved in a solvent. Specific examples of the solvent include methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, and isopropanol. The solvent is not limited to a single solvent and may be a mixed solvent of two or more kinds.

  The resin composition of the present invention may contain a chain transfer agent. Specific examples of the chain transfer agent include n-dodecyl mercaptan, mercaptoisobutyl alcohol, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol, glycidyl mercaptan, α -Methylstyrene dimer, carbon tetrachloride, chloroform, hydroquinone and the like.

  The resin composition of the present invention may contain a tackifying resin. Specific examples of the tackifying resin include rosin-based resins, rosin phenol-based resins, polymerized rosin-based resins, polymerized rosin ester-based resins, hydrogenated rosin ester-based resins, disproportionated rosin ester-based resins, terpene-based resins, and terpene phenols. Examples thereof include a system resin, an aliphatic hydrocarbon resin, an aliphatic petroleum resin, an aromatic petroleum resin, a hydrogenated petroleum resin, and an alkylphenol formaldehyde resin (oil-based phenol resin). These may be used alone or in combination of two or more.

  The resin composition of the present invention may contain a crosslinking agent. Specific examples of the cross-linking agent include an isocyanate compound, an epoxy compound, an aziridine compound, a polyvalent metal salt, a metal chelate, a keto hydrazide compound, an oxazoline compound, a silane compound, and a glycidyl (alkoxy) epoxysilane compound.

  The resin composition of the present invention may contain a polymerization initiator. Specific examples of the polymerization initiator include an azo-based polymerization initiator, a persulfate-based polymerization initiator, a peroxide-based polymerization initiator, a carbonyl-based polymerization initiator, and a redox such as a combination of a persulfate and sodium hydrogen sulfite. Examples include a system polymerization initiator and the like.

  The resin composition of the present invention can be suitably used as an adhesive, a pressure-sensitive adhesive, a sealing material, an ink composition and the like. Adhesives, pressure-sensitive adhesives, sealants, and ink compositions containing the reaction product of the resin composition of the present invention have good affinity for polyolefin substrates, and are therefore expected to have excellent adhesion to polyolefin substrates. To be done.

  Since the resin composition of the present invention contains a (meth) acryloyl group-containing compound as an acrylic monomer, by polymerizing the monomer by radical polymerization, the reaction product of the resin composition of the present invention can be used as an adhesive or adhesive. It can be used for applications such as agents.

  Further, the resin composition of the present invention is excellent in dispersibility of the modified olefin polymer in the acrylic monomer even if the modified olefin polymer is not in the form of an aqueous emulsion, but from the viewpoint of handleability, The resin composition of the present invention may be dispersed in an aqueous solvent to form an aqueous emulsion. The aqueous emulsion can be used as an adhesive or a tacky adhesive, and it can be used as an adhesive or a tacky adhesive by applying the aqueous emulsion to a polyolefin substrate and then polymerizing a monomer by radical polymerization. it can.

  Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Intrinsic viscosity [η]>
Viscometer "VMR-053U-PC-F01" (manufactured by Sogo Co., Ltd.), Ubbelohde type viscous tube (timer sphere volume: 2-3 mL, capillary tube diameter: 0.44-0.48 mm), tetralin as a solvent A 0.02 to 0.16 g / dL solution was measured at 135 ° C.

<DSC measurement>
(1) Melting point (Tm-D) and melting endotherm (ΔH-D)
Using a differential scanning calorimeter "DSC-7" (manufactured by Perkin-Elmer Co.), 10 mg of a sample was kept under a nitrogen atmosphere at -10 ° C for 5 minutes, and then heated at 10 ° C / minute to obtain a melt. The melting endotherm (ΔHD) was calculated from the endothermic curve. Further, the melting point (Tm-D) was determined from the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve.
The melting endotherm (ΔH-D) includes a peak of a melting endotherm curve obtained by using a line connecting a point on the low temperature side where the calorific value does not change and a point on the high temperature side where the calorific value does not change as a baseline. It was calculated by calculating the area surrounded by the line portion and the baseline.

(2) Semi-crystallization time Using a differential scanning calorimeter "DSC-7" (manufactured by Perkin Elmer Co.), 10 mg of the sample was held at 25 ° C for 5 minutes and heated to 220 ° C at 320 ° C / sec. After being held for a minute, the temperature was cooled to 25 ° C. at 320 ° C./sec and held for 5 hours to measure the time change of the amount of heat generated during the isothermal crystallization process. When the integrated value of the calorific value from the start of the isothermal crystallization to the completion of the crystallization is 100%, the time from the start of the isothermal crystallization to the integrated value of the calorific value of 50% is obtained as the half crystallization time. It was

<GPC measurement>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by the gel permeation chromatography (GPC) method, and the molecular weight distribution (Mw / Mn) was obtained. For the measurement, the following equipment and conditions were used to obtain a polystyrene-equivalent weight average molecular weight and number average molecular weight. The molecular weight distribution (Mw / Mn) is a value calculated from these weight average molecular weight (Mw) and number average molecular weight (Mn).
(GPC measuring device)
Column: "TOSO GMHHR-H (S) HT" manufactured by Tosoh Corporation
Detector: RI detection for liquid chromatogram "WATERS 150C" manufactured by Waters Corporation
(Measurement condition)
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL
Injection volume: 160 μL
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

<NMR measurement>
In the propylene-based polymer of the present invention, ¹³ C-NMR spectrum was measured under the following apparatus and conditions to determine [mmmm], [rrrr], [rmrm] and [mm]. The attribution of peaks was according to the method proposed in "Macromolecules, 8, 687 (1975)" by A. Zambelli and the like.
Apparatus: JEOL Ltd., JNM-EX400 type ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / mL
Solvent: 1,2,4-trichlorobenzene / heavy benzene (volume ratio 90/10) mixed solvent Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

(a formula)
M = m / S × 100
R = γ / S × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7 to 22.5 ppm

Further, in the butene-based polymer of the present invention, ¹³ C-NMR spectrum was measured by the following apparatus and conditions to determine [mmmm], [rrrr], [rmrm] and [mm]. The attribution of peaks is described in "Polymer Journal, 16, 717 (1984)" by Asakura et al., J. "Macromol. Chem. Phys., C29, 201 (1989)" reported by Randall et al. It was determined according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al. That is, the signals of methylene group and methine group were measured using ¹³ C-NMR spectrum, and [mmmm], [rrrr], [rmrm] and [mm] in the butene polymer molecule were determined.
^{The 13} C-NMR spectrum was measured under the same equipment and conditions as those used for NMR in the above-mentioned propylene polymer, except that the concentration was changed to 230 mg / mL.

The butene content when the olefin polymer was a propylene / butene copolymer was measured as follows.
The butene content was calculated by the following method, using a JNM-EX400 type NMR apparatus manufactured by JEOL Ltd. to measure ¹³ C-NMR spectrum under the following conditions.
Sample concentration: 220mg / mL
Solvent: 1,2,4-trichlorobenzene / heavy benzene (volume ratio 90/10) mixed solvent Measuring temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 10 seconds Accumulation frequency: 4,000 times Under the above conditions, PP, PB, and BB chains were prepared according to J. C. According to the method proposed by Randall, Macromolecules, 1978, 11, 592, the signal of Sαα carbon in the 13C nuclear magnetic resonance spectrum was measured, and the PP, PB, BB diad chain fraction in the copolymer molecular chain was determined. It was The butene content was determined by the following formula from each of the obtained diat chain fractions (mol%).
Butene content (mol%) = ([BB] + [PB]) / 2
([PP] represents a propylene-propylene chain fraction, [BB] represents a butene-butene chain fraction, and [PB] represents a propylene-butene chain fraction.)

<Acid value>
The acid value was measured based on JIS K2501: 2003.

Production example 1
[Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride]
Under a nitrogen stream, 2.5 g (7.2 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) and 100 mL of ether were added to a 200 mL Schlenk bottle.
After cooling to −78 ° C. and 9.0 mL (14.8 mmol) of a hexane solution of n-butyllithium (n-BuLi) (1.6 mol / liter), the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the obtained solid was washed with 20 mL of hexane and dried under reduced pressure to quantitatively obtain a lithium salt as a white solid.
In a Schlenk bottle, a lithium salt (6.97 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) was dissolved in 50 mL of THF (tetrahydrofuran), and iodomethyltrimethylsilane was added at room temperature. 2.1 mL (14.2 mmol) was slowly added dropwise, and the mixture was stirred for 12 hours.
The solvent was distilled off, 50 mL of ether was added, and the mixture was washed with a saturated ammonium chloride solution.
After liquid separation, the organic phase was dried and the solvent was removed to obtain (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) 3.04 g (5.9 mmol) Got (Yield 84%)
Next, in a Schlenk bottle under a nitrogen stream, 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above was obtained. And 50 mL of ether were added. After cooling to −78 ° C. and adding hexane solution (1.6 mol / L) of n-butyllithium (n-BuLi) in 7.4 mL (11.8 mmol), the mixture was stirred at room temperature for 12 hours. The solvent was evaporated, and the obtained solid was washed with 40 mL of hexane to obtain 3.06 g of a lithium salt as an ether adduct.
Under a nitrogen stream, 3.06 g of the lithium salt obtained above was suspended in 50 mL of toluene. This was cooled to -78 ° C, and a toluene (20 mL) suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride previously cooled to -78 ° C was added dropwise thereto. After the dropping, the mixture was stirred at room temperature for 6 hours. After distilling off the solvent of this reaction solution, the obtained residue was recrystallized from dichloromethane to obtain (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl). 0.9 g (1.33 mmol) of yellow fine crystals of zirconium dichloride were obtained (yield 26%).
When the ¹ H-NMR of the yellow fine crystals obtained above was determined, the following results were obtained.
¹ H-NMR (90 MHz, CDCl ₃ ): δ0.0 (s, -SiMe _3- , 18H), 1.02, 1.12 (s, -Me ₂ Si-, 12H), 2.51 (dd, _{-CH 2 -, 4H), 7.1-7.6} (m, Ar-H, 8H)

Production example 2
(Production of polybutene-1)
In a heat-dried 2 L autoclave, 600 mL of heptane, 0.6 mmol of triisobutylaluminum, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) obtained in Production Example 1 ) 5.0 μmol of zirconium dichloride and 15.0 μmol of dimethylanilinium tetrakispentafluorophenyl borate were added, and 0.02 MPa of hydrogen was further introduced. While increasing the polymerization temperature to 60 ° C., butene-1 was pressured up to 0.24 MPa in total pressure to carry out polymerization for 60 minutes. After the completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 55 g of polybutene-1.
The obtained polybutene-1 has an intrinsic viscosity [η] of 0.58 dL / g, a weight average molecular weight Mw of 68,000, a molecular weight distribution Mw / Mn of 1.8, and stereoregularity (mesopentad fraction [mmmm]). 67.8 mol%, melting point Tm-D was 68.4 ° C.

Production Example 3
(Production of Maleic Anhydride Modified Polybutene-1)
Nitrogen introduction tube, Dimroth tube and a 0.5L separa flask equipped with a stirrer, polybutene-1 30g obtained in Production Example 2 was charged, under a nitrogen atmosphere, using an oil bath, heated to 140 ℃, After the temperature was raised, the contents were melted and stirring was started. Thereafter, 3 g of maleic anhydride and 0.3 g of "Perhexa 25B" (manufactured by NOF CORPORATION) were added, the temperature was raised to 150 ° C, and the mixture was stirred for 1 hour. The temperature was further raised to 160 ° C., and the mixture was stirred for 30 minutes. After cooling, the obtained reaction product was dried under heating and reduced pressure to obtain the target product.
The maleic anhydride-modified polybutene-1 thus obtained had an intrinsic viscosity [η] of 0.49 dL / g, a weight average molecular weight Mw of 65,300, a number average molecular weight Mn of 26,100, and a molecular weight distribution Mw / Mn of 2.5. , Mesopentad fraction [mmmm] is 67.5 mol%, [mm] is 83.7 mol%, [rmrm] is 1.7 mol%, [rrrr] / (1- [mmmm]) is 0.92, The melting point Tm-D was 69.1 ° C., the melting endotherm ΔH-D was 35.7 J / g, the acid value was 61 mgKOH / g, and the half-crystallization time was 52 minutes.

Production Example 4
(Production of polypropylene)
400 mL of heptane was charged into an autoclave having an internal volume of 1 L under a nitrogen stream, and 0.15 mL (2 mol / L, 0.3 mmol) of a heptane solution of triisobutylaluminum was charged at room temperature. Further, hydrogen was introduced at 0.15 MPa and propylene was introduced at a total pressure of 0.85 MPa. Then, the temperature was raised to 70 ° C. with stirring, and 0.08 mL of a toluene solution of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride (10 μmol / mL) and 0.20 mL (20 μmol / mL) of a heptane slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate were charged and polymerization was carried out for 30 minutes. After completion of the reaction, the reaction product was dried under reduced pressure to obtain 135 g of polypropylene.

Production Example 5
(Production of maleic anhydride modified polypropylene)
To a 0.5 L separa flask equipped with a nitrogen introducing tube, a Dimroth tube, and a stirrer, 60 g of the polypropylene obtained in Production Example 4 and 6 g of maleic anhydride were charged, and under a nitrogen atmosphere, an oil bath was used to raise the temperature to 130 ° C. After heating and raising the temperature, stirring was started after the contents were melted. Thereafter, 0.6 g of "Perhexa 25B" (manufactured by NOF CORPORATION) was added, the temperature was raised to 150 ° C, and the mixture was stirred for 1 hour. The target product was obtained by drying the obtained reaction product under heating and reduced pressure.
The maleic anhydride-modified polypropylene thus obtained had an intrinsic viscosity [η] of 0.65 dL / g, a weight average molecular weight Mw of 59,500, a molecular weight distribution Mw / Mn of 2.3, and a mesopentad fraction [mmmm] of 48.1. Mol%, [mm] is 69.3 mol%, [rmrm] is 2.5 mol%, [rrrr] / (1- [mmmm]) is 0.04, melting point Tm-D is 78.2 ° C., melting The endothermic amount ΔH-D was 36.2 J / g, the acid value was 69 mgKOH / g, and the half-crystallization time was 21 minutes.

Production Example 6
(Production of Propylene / Butene-1 Copolymer)
In a heat-dried 1 L autoclave, heptane 200 mL, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethyl-indenyl) zirconium dichloride toluene solution 0.05 mL (10 μmol / mL) Then, 0.38 mL (1.3 mmol / mL) of a toluene slurry of methylalumoxane, 200 mL of butene-1 and 0.5 mmol of triisobutylaluminum were added, and 0.03 MPa of hydrogen was further introduced. While stirring, the temperature was raised to 60 ° C., propylene was introduced, and the mixture was continuously fed at a total pressure of 0.5 MPa and polymerized for 30 minutes. After the completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 21 g of a propylene / butene-1 copolymer.

Production Example 7
(Production of maleic anhydride-modified propylene / butene-1 copolymer)
20 g of the propylene / butene-1 copolymer obtained in Production Example 6 and 2 g of maleic anhydride were placed in a 0.5 L separa flask equipped with a nitrogen introducing tube, a Dimroth tube, and a stirrer, and an oil bath was added under a nitrogen atmosphere. The temperature was raised to 130 ° C. by using, and after the content was melted, stirring was started. Thereafter, 0.1 g of "Perhexa 25B" (manufactured by NOF CORPORATION) was added, the temperature was raised to 150 ° C, and the mixture was stirred for 1 hour. The target product was obtained by drying the obtained reaction product under heating and reduced pressure.
The obtained maleic anhydride-modified propylene / butene-1 copolymer had an intrinsic viscosity [η] of 0.69 dL / g, a weight average molecular weight Mw of 65,500, a molecular weight distribution Mw / Mn of 2.2, and propylene / butene. The molar ratio of -1 is 3.3 mol% / 96.7 mol%, [mm] is 82.9 mol%, melting point Tm-D is 56.2 ° C, and melting endotherm ΔH-D is 31.0 J / g. The acid value was 55 mgKOH / g, and the half-crystallization time was 74 minutes.

Example 1
Into a 0.3 L separa flask equipped with a nitrogen introducing tube, a Dimroth tube, and a stirrer, 2.5 g of maleic anhydride-modified polybutene-1 obtained in Production Example 3 and 47.5 g of 2-ethylhexyl acrylate were charged, and a nitrogen atmosphere was applied. Then, using an oil bath, the temperature was raised to 120 ° C. and the mixture was stirred for 30 minutes to obtain a uniform resin composition solution.
Even when 100 mL of the obtained solution was transferred to a sample bottle and allowed to stand at 5 ° C. for 2 hours, there was no particular change in precipitation and the like, and a uniform solution was maintained.

Example 2
The procedure of Example 1 was repeated except that the maleic anhydride-modified polybutene-1 obtained in Production Example 3 was replaced with the maleic anhydride-modified polypropylene obtained in Production Example 5. A resin composition solution was obtained.
Even when 100 mL of the obtained solution was transferred to a sample bottle and allowed to stand at 5 ° C. for 2 hours, there was no particular change in precipitation and the like, and a uniform solution was maintained.

Example 3
Example 1 except that the maleic anhydride-modified polypropylene / butene-1 copolymer obtained in Production Example 7 was used in place of the maleic anhydride-modified polybutene-1 obtained in Production Example 3. A uniform resin composition solution was obtained in the same manner as in.
Even when 100 mL of the obtained solution was transferred to a sample bottle and allowed to stand at 5 ° C. for 2 hours, there was no particular change in precipitation and the like, and a uniform solution was maintained.

Example 4
A uniform resin composition solution was obtained in the same manner as in Example 1 except that 45 g of 2-ethylhexyl acrylate and 2.5 g of acrylamide were used instead of 47.5 g of 2-ethylhexyl acrylate.
Even when 100 mL of the obtained solution was transferred to a sample bottle and allowed to stand at 5 ° C. for 2 hours, there was no particular change in precipitation and the like, and a uniform solution was maintained.

Comparative Example 1
A homogeneous resin composition was obtained in the same manner as in Example 1 except that the polybutene-1 obtained in Production Example 2 was used instead of the maleic anhydride-modified polybutene-1 obtained in Production Example 3. A product solution was obtained.
When 100 mL of the obtained solution was transferred to a sample bottle and allowed to stand at 5 ° C. for 2 hours, polybutene-1 was precipitated and became cloudy.

Comparative example 2
A homogeneous resin composition solution was obtained in the same manner as in Example 1 except that the polypropylene obtained in Production Example 4 was used in place of the maleic anhydride-modified polybutene-1 obtained in Production Example 3. Got
When 100 mL of the obtained solution was transferred to a sample bottle and allowed to stand at 5 ° C. for 2 hours, polypropylene was precipitated and became cloudy.

Comparative Example 3
In the same manner as in Example 1 except that the polypropylene / butene-1 copolymer obtained in Production Example 6 was used instead of the maleic anhydride-modified polybutene-1 obtained in Production Example 3. A uniform resin composition solution was obtained.
When 100 mL of the obtained solution was transferred to a sample bottle and allowed to stand at 5 ° C. for 2 hours, a polypropylene / butene-1 copolymer was precipitated and became cloudy.

  As is clear from the results of Examples and Comparative Examples, the resin composition of the present invention containing a modified olefin polymer having a specific structure and physical properties was prepared by adding (meth) acryloyl group-containing compound (acrylic monomer) to It can be seen that the modified olefin polymer has excellent dispersibility.

  The resin composition of the present invention has excellent dispersibility of the modified olefin polymer in the acrylic monomer. Therefore, the resin composition of the present invention has a good affinity for polyolefin and is suitable for applications such as adhesives, pressure-sensitive adhesives, sealing materials, and ink compositions.

Claims (12)

(A) below as the component (1) to the modified olefin polymer satisfying (3), viewed contains a component (B) as one or more (meth) acryloyl group-containing compound,
The modified olefin polymer is obtained by acid-modifying an olefin polymer with an organic acid,
The amount of acid modification of the modified olefin polymer is 0.1 to 20% by mass,
The amount of the component (A) is 0.1% by mass or more and 50% by mass or less based on 100% by mass of the total amount of the components (A) and (B).
Non-aqueous resin composition.
(1) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 2.5 dL / g.
(2) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./minute to obtain the highest temperature side of the melting endothermic curve. The melting point (Tm-D) defined as the peak top of the observed peak is not observed or is 0 to 100 ° C.
(3) The half-crystallization time measured by a differential scanning calorimeter (DSC) is 3 minutes or longer, or the crystallization peak measured by a differential scanning calorimeter (DSC) is not observed. The non-aqueous resin composition according to claim 1, wherein the modified olefin polymer satisfies the following (4).
(4) Using a differential scanning calorimeter (DSC), the sample was held in a nitrogen atmosphere at −10 ° C. for 5 minutes and then heated at 10 ° C./minute to obtain a melting endotherm obtained from a melting endotherm curve. The amount of heat (ΔH-D) is 0 to 80 J / g. The non-aqueous resin composition according to claim 1 or 2, wherein the modified olefin polymer satisfies the following (5).
(5) The acid value is 10 to 250 mgKOH / g. The non-aqueous resin composition according to any one of claims 1 to 3, wherein the modified olefin polymer satisfies the following (6).
(6) The mesotriad fraction [mm] is 55 to 90 mol%. The non-aqueous resin composition according to any one of claims 1 to 4, wherein the modified olefin polymer satisfies the following (7) and (8).
(7) The mesopentad fraction [mmmm] is 20 to 80 mol%.
(8) [rrrr] / (1- [mmmm]) is 3.0 or less. 50 mol% or more of the monomer which comprises the said modified olefin polymer is at least 1 sort (s) selected from the group which consists of a propylene monomer and 1-butene monomer, The any one of Claims 1-5. Non-aqueous resin composition. The (meth) acryloyl group-containing compound is a compound represented by the following general formula (I) or (II), non-aqueous resin composition according to any one of claims 1-6.

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom, an alkyl group, a hetero atom-containing group, an aromatic group, or an alkoxy (poly) alkylene oxide group. ] The reaction of the non-aqueous resin composition according to any one of claims 1-7. An adhesive containing the reactant according to claim 8 . An adhesive containing the reactant according to claim 8 . A sealing material containing the reactant according to claim 8 . An ink composition comprising the reaction product according to claim 8 .