JP2018076454A - Propylene-based polymer, propylene-based resin composition, and hot-melt adhesive containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot-melt adhesive which has an improved adhesive strength while maintaining or improving fluidity.SOLUTION: There are provided: [1] a propylene-based polymer having a melting endotherm (ΔH-D) measured by a differential scanning calorimeter (DSC) of 0-80 J/g and a viscosity measured by a B-type viscometer at 190°C of 500-6,000 mPa s; [2] a propylene-based resin composition containing a resin (A) containing the propylene-based polymer, and a plasticizer (B); and [3] a hot-melt adhesive containing the propylene-based polymer or the propylene-based resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a propylene polymer, a propylene resin composition, and a hot melt adhesive containing them.

  The hot-melt adhesive is a solventless adhesive, and is applied to an adherend by heating and melting, and then solidified by cooling and expresses adhesiveness. In recent years, hot-melt adhesives are excellent in high-speed coating properties, fast curing properties, solvent-free properties, barrier properties, energy savings, economic efficiency, and the like, and thus are widely used in various fields.

  As a base polymer of a hot melt adhesive, a propylene-based polymer is widely used from the viewpoint of thermal stability. Among them, low molecular weight polypropylene polymerized with a metallocene-based catalyst has high fluidity, excellent coating properties when used as a hot melt adhesive, excellent adhesion strength of low-polar substances such as polypropylene, and heat stability during heat melting Because of its excellent properties, it can be suitably used as a base polymer for various hot melt adhesives (Patent Documents 1 and 2).

International Publication No. 2014/192767 JP 2013-064056 A

  A hot melt adhesive containing a low molecular weight polypropylene polymerized by a metallocene catalyst as a base polymer is required to improve adhesive strength while maintaining or improving fluidity.

  Therefore, the problem to be solved by the present invention is to provide a hot-melt adhesive having improved adhesive strength while maintaining or improving fluidity.

  As a result of intensive studies, the present inventors have increased the amount of high molecular weight resin such as styrene-butadiene-styrene (SBS) thermoplastic elastomer when conventional low molecular weight polypropylene is used as the base polymer. In this case, it was found that although the adhesive strength of the hot melt adhesive can be improved, the fluidity is greatly reduced. In research and development of hot melt adhesives, it is required to improve adhesive strength while maintaining or improving fluidity. Therefore, as a result of further earnest research, the present inventors have developed a propylene-based polymer having a specific low viscosity, and using the propylene-based polymer as a base polymer solves the above problem. I found it. The present invention has been completed based on such findings.

That is, the present disclosure relates to the following.
<1> The melting endotherm (ΔH-D) measured with a differential scanning calorimeter (DSC) is 0 to 80 J / g, and the viscosity measured with a B-type viscometer at 190 ° C. is 500 to 6,000 mPa -Propylene polymer which is s.
<2> The propylene-based polymer according to <1>, which satisfies at least one of the following (i) and (ii).
(I) The structural unit of ethylene is contained in an amount exceeding 0 mol% and not more than 35 mol%.
(Ii) The structural unit of 1-butene is contained in an amount of more than 0 mol% and 45 mol% or less.
<3> The propylene-based polymer according to <1> or <2>, which satisfies the following (1).
(1) Mesopentad fraction [mmmm] is 20 mol% or more and 80 mol% or less.
<4> The propylene-based polymer according to any one of <1> to <3>, which satisfies the following (2).
(2) The value of [rrrr] / (1- [mmmm]) is 0.1 or less.
<5> A propylene-based resin composition containing a resin (A) and a plasticizer (B),
The resin (A) includes the propylene polymer (A-1) according to any one of the above <1> to <4>, and the content of the plasticizer (B) is the resin (A ) A propylene-based resin composition that is 5 to 200 parts by mass with respect to 100 parts by mass.
<6> The propylene-based resin composition according to <5>, wherein the plasticizer (B) is oil or wax.
<7> The above <5> or further containing a tackifier (C), wherein the content of the tackifier (C) is 10 to 500 parts by mass with respect to 100 parts by mass of the resin (A). <6> The propylene-based resin composition according to item 6.
<8> The propylene-based resin composition according to <7>, wherein the tackifier (C) has a softening point of -20 to 180 ° C.
<9> The resin (A) includes the propylene polymer (A-1) and a thermoplastic resin (A-2) other than the propylene polymer (A-1).
The mass ratio ((A-1) / (A-2)) between the propylene polymer (A-1) and the thermoplastic resin (A-2) is 5/95 to 99/1, < The propylene-based resin composition according to any one of 5> to <8>.
<10> The thermoplastic resin (A-2) is at least one selected from the group consisting of a styrene block copolymer, an ethylene vinyl acetate copolymer, an ethylene olefin polymer, an amorphous polyolefin, and a propylene elastomer. The propylene-based resin composition according to <9>, including
<11> The thermoplastic resin (A-2) includes a styrene block copolymer or an ethylene vinyl acetate copolymer, and the content of the tackifier (C) is 100 parts by mass of the resin (A). The propylene-based resin composition according to <10>, which is 40 to 400 parts by mass with respect to the above.
<12> The thermoplastic resin (A-2) contains an ethylene-based olefin polymer or an amorphous polyolefin, and the content of the tackifier (C) is 30 with respect to 100 parts by mass of the resin (A). The propylene-type resin composition as described in said <10> which is -350 mass parts.
<13> The thermoplastic resin (A-2) contains a propylene-based elastomer, and the content of the tackifier (C) is 10 to 300 parts by mass with respect to 100 parts by mass of the resin (A). The propylene-based resin composition according to <10> above.
<14> A hot melt containing the propylene polymer according to any one of the above <1> to <4> or the propylene resin composition according to any one of the above <5> to <13>. adhesive.

  The propylene-based polymer of one embodiment of the present disclosure and the propylene-based resin composition containing the same can improve the fluidity and interfacial adhesive strength of the hot-melt adhesive. In addition, the hot melt adhesive according to one embodiment of the present disclosure can increase the blending amount of the high molecular weight resin, and can improve the interfacial adhesive strength while maintaining fluidity. Furthermore, in the hot melt adhesive of one embodiment of the present disclosure, the material strength is suppressed by improving the tensile strength at break, and the adhesive strength can be improved from the side.

  Hereinafter, the present invention will be described in detail. In this specification, the term “A to B” relating to the description of numerical values means “A or more and B or less” (when A <B) or “A or less and B or more” (when A> B). . Moreover, in this invention, the combination of a preferable aspect is a more preferable aspect.

[Propylene polymer (A-1)]
The propylene-based polymer of the present invention (hereinafter also referred to as “propylene-based polymer (A-1)”) has a melting endotherm (ΔHD) measured by a differential scanning calorimeter (DSC) of 0 to 0. The viscosity is 80 J / g and the viscosity measured with a B-type viscometer at 190 ° C. is 500 to 6,000 mPa · s.

  The propylene polymer (A-1) is at least one selected from a propylene homopolymer and a copolymer of propylene and another olefin. The propylene structural unit content in the propylene polymer (A-1) is preferably 50 mol% or more, more preferably 65 mol% or more, still more preferably 75 mol% or more, and even more preferably 80 mol% or more. It is.

  Examples of olefins other than propylene that can be contained in the propylene polymer (A-1) include ethylene and α-olefins having 4 or more carbon atoms. The α-olefin having 4 or more carbon atoms is preferably an α-olefin having 4 to 24 carbon atoms, more preferably an α-olefin having 4 to 12 carbon atoms, and still more preferably an α-olefin having 4 to 8 carbon atoms. . Specific examples of the α-olefin include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. In this invention, 1 type, or 2 or more types can be used among these.

  Examples of the propylene polymer (A-1) include a propylene homopolymer, a propylene-ethylene block copolymer, a propylene-butene block copolymer, a propylene-α-olefin block copolymer, and a propylene-ethylene random copolymer. , A propylene-based polymer selected from propylene-butene random copolymer, propylene-α-olefin random copolymer, propylene-α-olefin graft copolymer, etc., and propylene homopolymer and propylene -An ethylene block copolymer is more preferable, and a propylene homopolymer is still more preferable.

  When the propylene polymer (A-1) is a copolymer containing a structural unit derived from ethylene, the content of the structural unit of ethylene in the propylene polymer (A-1) is preferably 0 mol. % To 35 mol% or less, more preferably more than 0 mol% to 30 mol% or less, still more preferably more than 0 mol% to 20 mol% or less, still more preferably more than 0 mol% to 15 mol% or less. In the case where the propylene-based polymer (A-1) is a copolymer containing a structural unit derived from an α-olefin having 4 or more carbon atoms, the propylene-based polymer (A-1) has 4 or more carbon atoms. The content of the constituent unit of α-olefin is preferably more than 0 mol% and 45 mol% or less, more preferably more than 0 mol% and 30 mol% or less, still more preferably more than 0 mol% and 20 mol% or less. .

When the propylene polymer (a1) is a copolymer, it is more preferable to satisfy at least one of the following (i) and (ii).
(I) The structural unit of ethylene is contained in an amount exceeding 0 mol% and not more than 35 mol%.
(Ii) The structural unit of 1-butene is contained in an amount of more than 0 mol% and 45 mol% or less.

  From the viewpoint of improving the fluidity and low-temperature coatability of the resin composition while maintaining the tensile strength at break of the resin composition containing the propylene polymer (A-1), the propylene polymer (A-1) is The following melting endotherm (ΔH-D) and melt viscosity (B-type viscosity) are preferable, and preferably have the following properties.

(Melting endotherm (ΔH-D))
The melting endotherm (ΔH-D) of the propylene-based polymer (A-1) is 0 J / g or more and 80 J / g or less, preferably 5 J / g, from the viewpoint of improving the solidification rate, flexibility and elongation at break. Above, more preferably 10 J / g or more, still more preferably 20 J / g, and preferably 70 J / g or less, more preferably 60 J / g or less, still more preferably 50 J / g or less.
The melting endotherm (ΔH−D) can be controlled by appropriately adjusting the monomer concentration and reaction pressure.
The melting endotherm (ΔH-D) is a melting endotherm curve obtained by DSC measurement with a line connecting a point on the low temperature side where there is no change in calorie and a point on the high temperature side where there is no change in calorie as a baseline. It is calculated by obtaining the area surrounded by the line portion including the peak observed on the highest temperature side and the base line.

(Melt viscosity (B type viscosity))
The melt viscosity of the propylene polymer (A-1) measured at 190 ° C. with a B-type viscometer is 500 mPa · s or more and 6,000 mPa · s or less from the viewpoint of improving fluidity and low-temperature coating property. When the melt viscosity of the propylene polymer (A-1) is within the above range, the fluidity and low temperature coating property of the propylene resin composition containing the propylene polymer (A-1) can be improved. The melt viscosity is preferably 1,000 mPa · s or more, more preferably 1,200 mPa · s or more, still more preferably 1,500 mPa · s or more, and preferably 5,000 mPa · s or less, more preferably It is 4,000 mPa · s or less, more preferably 3,000 mPa · s or less.
The melt viscosity is specifically measured by the method described in Examples.

The propylene-based polymer (A-1) preferably satisfies any one of the following (1) and (2), or both, and more preferably at least one of the following (3) to (5) More preferably, all of the following (1) to (5) are satisfied.
(1) Mesopentad fraction [mmmm] is 20 mol% or more and 80 mol% or less.
(2) The value of [rrrr] / (1- [mmmm]) is 0.1 or less.
(3) Racemic meso racemic meso pentad fraction [rmrm] exceeds 2.5 mol%.
(4) The value of [mm] × [rr] / [mr] ² is 2.0 or less.
(5) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the observed peak top is 0 ° C. or higher and 120 ° C. or lower.

(1) Mesopentad fraction [mmmm]
The mesopentad fraction [mmmm] is an index representing the stereoregularity of the propylene-based polymer, and the stereoregularity increases as the mesopentad fraction [mmmm] increases. The mesopentad fraction [mmmm] of the propylene polymer (A-1) is preferably 20 mol% or more, more preferably 25 mol% or more, and further preferably 30 mol% or more, from the viewpoints of flexibility and fluidity. And preferably 80 mol% or less, more preferably 70 mol% or less, and still more preferably 65 mol% or less.

(2) [rrrr] / (1- [mmmm])
The value of [rrrr] / (1- [mmmm]) is obtained from the mesopentad fraction [mmmm] and the racemic pentad fraction [rrrr] and is an index indicating the uniformity of the regular distribution of the propylene-based polymer. . Increasing this value of [rrrr] / (1- [mmmm]) results in a mixture of highly stereoregular polypropylene and atactic polypropylene like conventional polypropylene produced using existing catalyst systems. If the value of [rrrr] / (1- [mmmm]) is within the above range, stickiness can be further suppressed. The units of the mesopentad fraction [mmmm] and the racemic pentad fraction [rrrr] are both mol%.
The value of [rrrr] / (1- [mmmm]) in the propylene polymer (A-1) is preferably 0.1 or less, more preferably 0.05 or less, still more preferably from the viewpoint of stickiness. 0.04 or less. Although a lower limit is not specifically limited, Preferably it is 0.001 or more, More preferably, it is 0.01 or more.

(3) Racemic meso racemic meso pentad fraction [rmrm]
The racemic meso racemic meso pentad fraction [rmrm] is an index that represents the randomness of the stereoregularity of the propylene polymer, and the randomness of the propylene polymer increases as the value increases.
The racemic meso racemic meso pentad fraction [rmrm] of the propylene polymer (A-1) is preferably more than 2.5 mol%, more preferably 2.6 mol% or more, and even more preferably 2.7 mol. % Or more. The upper limit is usually about 10 mol%, more preferably 7 mol% or less, still more preferably 5 mol% or less, and still more preferably 4 mol% or less.

(4) [mm] × [rr] / [mr] ²
The value of [mm] × [rr] / [mr] ² calculated from the mesotriad fraction [mm], the racemic triad fraction [rr] and the mesoracemi triad fraction [mr] is an indicator of the randomness of the polymer. The closer to 1, the higher the randomness. The units of mesotriad fraction [mm], racemic triad fraction [rr], and mesoracemitriad fraction [mr] are all mol%.
The value of the above formula in the propylene polymer (A-1) is preferably 2.0 or less, more preferably 1.8 or less, and still more preferably 1.6 or less. Although a lower limit is not specifically limited, Preferably it is 0.5 or more.

Here, the mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic meso racemic mesopentad fraction [rmrm] were determined by A. Zambelli et al., “Macromolecules, 6, 925 (1973). ) ”, And the meso fraction, the racemic fraction, and the racemic meso-racemic meso fraction in the pentad unit in the polypropylene molecular chain measured by the signal of the methyl group in the ¹³ C-NMR spectrum. is there. Further, the mesotriad fraction [mm], the racemic triad fraction [rr], and the mesoracemi triad fraction [mr] are a meso fraction, a racemic fraction, and a meso racemic fraction in triad units in the polypropylene molecular chain. These triad fractions are also calculated by the above method.

(5) Melting point (Tm-D)
The melting point (Tm-D) of the propylene polymer (A-1) is preferably 120 ° C. or less, more preferably 100 ° C. or less, from the viewpoint of the adhesive strength of the adhesive containing the propylene polymer (A-1). More preferably, it is 90 ° C. or less, and still more preferably 80 ° C. or less. In addition, the melting point is preferably 0 ° C. or higher, more preferably 40 ° C. or higher because of easy handling.
In the present invention, a differential scanning calorimeter (manufactured by Perkin Elmer, “DSC-7”) was used, and 10 mg of a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. Let the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by setting the melting point (Tm-D). The melting point can be controlled by appropriately adjusting the monomer concentration and reaction pressure.

(1,3-bond fraction)
The propylene polymer (A-1) preferably has a 1,3-bond fraction of less than 0.3 mol%, more preferably less than 0.1 mol%, and even more preferably 0 mol%. . When it is within the above range, the compatibility with the tackifier becomes good.
The control of the 1,3-bond fraction is performed according to the structure of the main catalyst and the polymerization conditions in the same manner as the control of the 2,1-bond fraction described later.

(2,1-bond fraction)
The propylene-based polymer (A-1) preferably has a 2,1-bond fraction of less than 0.3 mol%, more preferably less than 0.1 mol%, and even more preferably 0 mol%. . When it is within the above range, the compatibility with the tackifier becomes good.
The 2,1-bond fraction is controlled depending on the structure of the main catalyst and the polymerization conditions. Specifically, the structure of the main catalyst has a large effect, and the 2,1-bond can be controlled by narrowing the insertion field of the monomer around the central metal of the main catalyst. The number of 2,1-bonds can be increased. For example, a catalyst called half-metallocene type has a wide insertion field around the central metal, so that structures such as 2,1-bonds and long-chain branches are likely to be generated. Although suppression can be expected, in the case of the racemic type, the stereoregularity becomes high, and it is difficult to obtain an amorphous polymer as shown in the present invention. For example, even a racemic type as described later introduces a substituent at the 3-position with a double-bridged metallocene catalyst and controls the insertion site of the central metal to obtain an amorphous polymer with very few 2,1-bonds. be able to.

The 1,3-bond fraction and 2,1-bond fraction of the propylene-based polymer (A-1) can be calculated by the following formula from the measurement result of the ¹³ C-NMR spectrum.
1,3-bond fraction = (D / 2) / (A + B + C + D) × 100 (mol%)
2,1-bond fraction = {(A + B) / 2} / (A + B + C + D) × 100 (mol%)
A: integrated value of 15 to 15.5 ppm B: integrated value of 17 to 18 ppm C: integrated value of 19.5 to 22.5 ppm D: integrated value of 27.6 to 27.8 ppm

(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) of the propylene-based polymer (A-1) is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 25,000 or more, from the viewpoint of mechanical strength. And preferably it is 500,000 or less, More preferably, it is 200,000 or less, More preferably, it is 100,000 or less, More preferably, it is 50,000 or less.
In the present invention, the weight average molecular weight (Mw) is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

(Molecular weight distribution (Mw / Mn))
From the viewpoint of mechanical strength, the molecular weight distribution (Mw / Mn) of the propylene polymer (A-1) is preferably less than 3.0, more preferably 2.5 or less, still more preferably 2.2 or less. And preferably 1.2 or more, more preferably 1.5 or more.
In the present invention, the molecular weight distribution (Mw / Mn) is a value calculated from the polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC).

(Producing method of propylene polymer (A-1))
The propylene polymer (A-1) can be produced using, for example, a metallocene catalyst as described in WO2003 / 087172. In particular, those using a transition metal compound in which a ligand forms a cross-linked structure via a cross-linking group are preferred, and in particular, a transition metal compound that forms a cross-linked structure via two cross-linking groups and Metallocene catalysts obtained by combining promoters are preferred.

For example,
(I) General formula (I)

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure through A ¹ and A ² They may be the same or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, 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 as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]
And (ii) (ii-1) a compound capable of reacting with the transition metal compound of component (i) or a derivative thereof to form an ionic complex, and (ii-2) aluminoxane And a polymerization catalyst containing at least one component selected from the group consisting of:

  As the transition metal compound (i), a ligand is preferably a (1,2 ′) (2,1 ′) double-bridged transition metal compound, such as (1,2′-dimethylsilylene) ( 2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride.

  Specific examples of the compound of component (ii-1) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl tetraphenylborate (tri- n-butyl) ammonium, benzyl tetraphenylborate (tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), trikis (tetrafluorophenyl) borate triethyla Monium, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) borate Benzyl tetrakis (pentafluorophenyl) ammonium borate (tri-n-butyl), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid Methylanilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium, tetrakis (pentafluoropheny L) Trimethylanilinium borate, methyl pyridinium tetrakis (pentafluorophenyl) borate, benzyl pyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylaniline borate Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, Trakis (pentafluorophenyl) borate ferrocenium, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, tetrakis (pentafluorophenyl) silver borate, Tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium 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.

  Also, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride, etc. An olefin-based polymer (A) may be produced using a combination of these organoaluminum compounds.

  The propylene polymer (A-1) of the present invention can be suitably applied to the use of a hot melt adhesive. Generally, a hot melt adhesive contains a tackifier and a plasticizer in addition to a base polymer. The propylene polymer (A-1) of the present invention can be used as part or all of the base polymer. Further, the propylene polymer (A-1) of the present invention may be used as an adhesive exhibiting sufficient adhesiveness as a single substance without including a plasticizer and a tackifier depending on the type of adherend. You can also.

[Propylene-based resin composition]
The propylene-based resin composition of the present invention includes a resin (A) containing the propylene-based polymer (A-1) and a plasticizer (B), and the content of the plasticizer (B) is the resin. (A) It is 5-200 mass parts with respect to 100 mass parts.

(Resin (A))
The resin (A) in the propylene-based resin composition of the present invention contains a propylene-based polymer (A-1). By including the propylene-based polymer (A-1), the propylene-based resin composition of the present invention can improve fluidity and low-temperature coatability while maintaining the tensile strength at break. Moreover, the propylene-type resin composition of this invention can increase the compounding quantity of high molecular weight resin by including a propylene-type polymer (A-1), and has tensile fracture strength, without reducing fluidity | liquidity. Can be improved.

When the propylene-based resin composition of the present invention is applied as a hot melt adhesive, the resin (A) functions as a base polymer of the hot melt adhesive. From the viewpoint of adhesive strength, fluidity, and low temperature coating property of the hot melt adhesive, the resin (A) is composed of a propylene polymer (A-1) and a thermoplastic resin other than the propylene polymer (A-1) ( A-2).
The mass ratio ((A-1) / (A-2)) between the propylene polymer (A-1) and the thermoplastic resin (A-2) is the adhesive strength, fluidity and low temperature application of the hot melt adhesive. From the viewpoint of property, it is preferably 5/95 to 99/1, more preferably 10/90 to 95/5, still more preferably 20/80 to 90/10, still more preferably 30/70 to 85/15.

  The thermoplastic resin (A-2) is composed of a styrene block copolymer, an ethylene vinyl acetate copolymer, an ethylene olefin polymer, an amorphous polyolefin, and a propylene elastomer from the viewpoint of the adhesive strength of the hot melt adhesive. It is preferable to include at least one selected from the group consisting of

<Styrenic block copolymer>
In the present invention, the “styrene block copolymer” is a copolymer obtained by block copolymerization of a styrene compound and a conjugated diene compound, and usually has a styrene compound block and a conjugated diene compound block. If the hot-melt-adhesive aimed at by this invention can be obtained, it will not be restrict | limited in particular.

  Here, examples of the “styrene compound” include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene and vinylanthracene. it can. Styrene is particularly preferable. These styrenic compounds can be used alone or in combination.

  The “conjugated diene compound” means a diolefin compound having at least a pair of conjugated double bonds. Specific examples of the “conjugated diene compound” include 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene), 2,3-dimethyl-1,3-butadiene, and 1,3- Examples thereof include pentadiene and 1,3-hexadiene. 1,3-butadiene and 2-methyl-1,3-butadiene are particularly preferred. These conjugated diene compounds can be used alone or in combination.

  The styrenic block copolymer may be an unhydrogenated product or a hydrogenated product. Specific examples of the “unhydrogenated product of a styrene block copolymer” include those in which a block based on a conjugated diene compound is not hydrogenated. In addition, the “hydrogenated product of a styrenic block copolymer” specifically includes a block copolymer in which all or a part of the block based on the conjugated diene compound is hydrogenated.

  The ratio of hydrogenation of “the hydrogenated product of the styrenic block copolymer” can be indicated by “hydrogenation rate”. “Hydrogenation rate” of “hydrogenated product of styrenic block copolymer” is based on the total aliphatic double bonds contained in the block based on the conjugated diene compound. The ratio of double bonds converted to hydrogen bonds. This “hydrogenation rate” can be measured by an infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like.

Specific examples of the “unhydrogenated product of the styrene block copolymer” include, for example, a styrene-isoprene block copolymer (also referred to as “SIS”) and a styrene-butadiene block copolymer (also referred to as “SBS”). Specific examples of “hydrogenated styrenic block copolymer” include, for example, hydrogenated styrene-isoprene block copolymer (also referred to as “SEPS”) and hydrogenated styrene-butadiene block copolymer (“SEBS”). Also referred to).
Styrenic block copolymers can be used alone or in combination.

A commercial item can be used as a styrenic block copolymer, and each can be used alone or in combination.
For example, “Asaprene T-439”, “Asaprene T-436”, “Asaprene T-438”, “Asaprene N505”, “Tuff Tech H1121”, “Tuff Tech H1062”, “Tuff Tech H1052X” and “Taftech H1052X” manufactured by Asahi Kasei Corporation “Tufrene T125”; “TR2003”, “TR2500” and “TR2600” manufactured by JSR Corporation; “Steron 857” and “Steron 841A” manufactured by Firestone; “Clayton D1118” manufactured by Clayton Polymer, “ “Clayton G1654”, “Clayton G1726”; “Sol T166” manufactured by Enichem Co., Ltd .; “Quintac 3433N” and “Quintac 3421” manufactured by Zeon Corporation; “Septon 2002” manufactured by Kuraray And "Septon 2063" as an example (Both are trade names).

  From the viewpoint of the adhesive strength of the hot melt adhesive, the styrene block copolymer preferably has a styrene block content (styrene content) in the styrene block copolymer of 5 to 50% by mass, more preferably 10%. -40 mass%.

<Ethylene vinyl acetate copolymer>
As ethylene vinyl acetate copolymer (EVA) used for this invention, vinyl acetate (VA) content rate becomes like this. Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%. These ethylene vinyl acetate copolymer resins (EVA) may be used alone or in combination of two or more.

Commercially available ethylene vinyl acetate copolymer resins include “Ultrasen 684” manufactured by Tosoh Corporation (VA content 20% by mass, MFR = 2000, ring and ball softening temperature 80 ° C.), “Ultrasen 722” (VA Content 28% by mass, MFR = 400, ring and ball method softening temperature 82 ° C.), “Ultrasen 735” (VA content 28% by mass, MFR = 1000, ring and ball method softening temperature 85 ° C.), etc. Name).
In addition, MFR (melt flow rate) means what was measured on condition of 190 degreeC and load 21.18N based on JISK7210, and the ring and ball method softening temperature was measured based on JISK2207. Say things.

<Ethylene olefin polymer>
Specific examples of the ethylene-based olefin polymer include polyethylene and a copolymer of ethylene and an olefin having 3 to 10 carbon atoms. Although it will not specifically limit if it can be used as a base polymer of a hot-melt-adhesive, From an adhesive viewpoint of a hot-melt-adhesive, Preferably it is an ethylene-alpha-olefin copolymer. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene. , 1-octadecene, 1-eicosene and the like, and one or more of them can be used. Among these α-olefins, 1-octene is preferable. From the viewpoint of adhesiveness of the hot-melt adhesive, ethylene-1-octene copolymer is more preferable, and ethylene-1-octene copolymer containing 5 to 50% by mass of a structural unit derived from 1-octene is more preferable. It is a coalescence.

  The melting point of the ethylene-based olefin polymer is preferably 60 to 120 ° C., more preferably 60 to 90 ° C., from the viewpoint of heat resistant creep resistance. The melting point of the ethylene-based olefin polymer can be measured by differential scanning calorimetry. In addition, the amorphous thing among ethylene-type olefin polymers belongs to the amorphous polyolefin mentioned later.

  Commercially available ethylene-based olefin polymers include “Engage”, “Affinity”, “Infuse” manufactured by Dow Chemical Co., Ltd .; “Exact” manufactured by ExxonMobil Corporation “Tuffmer H”, “TAFMER A”, “TAFMER P” manufactured by Mitsui Chemicals, Inc .; “LUCENE” of LG Chemical Co., Ltd .; Nippon Polyethylene ( An example is “Kernel” manufactured by Co., Ltd. (all are trade names).

<Amorphous polyolefin>
The amorphous olefin polymer is one or more homopolymers or copolymers selected from the group consisting of linear or branched α-olefins or dienes having 2 to 24 carbon atoms, and is not particularly limited. , Polybutene, polybutadiene, polyisoprene, and amorphous polyalphaolefin.

  Examples of the polybutene include isobutene and normal butene each alone or as a copolymer and a hydrogenated product thereof. As a commercially available product of polybutene, “LV-7”, “LV-50”, “LV-100”, “HV-15”, “HV-35”, “HV-50” manufactured by JX Energy Corporation, “HV-100”, “HV-190”, “HV-300”, “SV-7000”, “Tetrax 3T”, “Tetrax 4T”, “Tetrax 5T”, “Tetrax 6T”, “High “Mall 4H”, “High Mall 5H”, “High Mall 5.5H”, “High Mall 6H”; “Nissan Polybutene 0N”, “Nissan Polybutene 06N”, “Nissan Polybutene 015N”, “ "Nissan Polybutene 3N", "Nissan Polybutene 5N", "Nissan Polybutene 10N", "Nissan Polybutene 30N", "Nissan Polybutene 200N"; "Gl" manufactured by BASF ssopal "; rice male Chemicals Co., Ltd." Indopol H-300 "," Indopol H-1900 "; ExxonMobil Chemical Co., Ltd. of" Parapol 950 "," Parapol 1300 ", and the like (all trade names).

Examples of the polybutadiene include 1,2-butadiene, 1,4-butadiene alone or a copolymer and a hydrogenated product thereof, and may have a hydroxyl group at the terminal. As commercial products of polybutadiene, “Nisso PB B-1000”, “Nisso PB B-2000”, “Nisso PB B-3000”, “Nisso PB BI-2000”, “Nisso PB BI” manufactured by Nippon Soda Co., Ltd. -3000 ";" PolyVEST 110 "," PolyVEST 130 "manufactured by Evonik, Inc .;" Ricon 130 "," Ricon 131 "," Ricon 134 "," Ricon 144 "," Ricon 150 "," Ricon "manufactured by Cray Valley “152”, “Ricon 153”, “Ricon 154”, “Ricon 156”, “Ricon 157”; “UBEPOL BR” series manufactured by Ube Industries, Ltd .; “JSR RB” series manufactured by JSR Corporation; "Nipo" manufactured by 1 BR ”series;“ Poly bd ^™ R-45HT ”,“ Poly bd ^™ R-15HT ”manufactured by Idemitsu Kosan Co., Ltd. (all are trade names).

Polyisoprene includes a homopolymer or copolymer of isoprene and a hydrogenated product thereof, and may have a hydroxyl group at the terminal. Commercially available products of polyisoprene include “Nipol IR” series manufactured by ZEON Corporation; “Kuraprene” series manufactured by Kuraray Co., Ltd .; “JSR IR” series manufactured by JSR Corporation; manufactured by Idemitsu Kosan Co., Ltd. “Poly ip ^™ ”, “EPOL ^™ ”, etc. (all are trade names).

  As an amorphous polyalphaolefin, the homopolymerization or copolymer of a C2-C6 olefin is mentioned. Commercially available products of amorphous polyalphaolefins include “Eastoflex” and “Aerafin” manufactured by Eastman; “REXtac” manufactured by REXtac; “Vestplast” manufactured by Evonik and the like (all are trade names).

<Propylene elastomer>
The propylene-based elastomer is an elastomer having a propylene unit as a main constituent unit. The elastomer is not limited by the density as long as it has rubber-elastic properties, and may be chemically cross-linked or non-chemically cross-linked.

  Commercially available propylene elastomers include “Tuffmer XM”, “Toughmer PN” and “Toughmer SN” manufactured by Mitsui Chemicals, Inc .; “Tough Selenium” manufactured by Sumitomo Chemical Co., Ltd .; Prime Polymer Co., Ltd. “Prime TPO” manufactured by Dow Chemical Co., Ltd. “Versify” manufactured by Dow Chemical Co., Ltd .; “Vistamaxx”, “Linxar” manufactured by ExxonMobil Co., Ltd., “Licocene” manufactured by Clariant, etc. “Adflex” manufactured by Basel (All are trade names).

  The thermoplastic resin (A-2) is not particularly limited as long as it is a thermoplastic resin other than the propylene polymer (A-1), and may include a thermoplastic resin other than those described above. For example, the melting endotherm (ΔH-D) measured with a differential scanning calorimeter (DSC) is 0 to 80 J / g, and the viscosity measured with a B-type viscometer at 190 ° C. is less than 500 mPa · s or 6 And a propylene-based polymer exceeding 1,000 mPa · s.

(Plasticizer (B))
Although it does not specifically limit as a plasticizer, What is used for a hot-melt-adhesive agent is preferable, More preferably, it is oil or wax. As the plasticizer, phthalic acid esters, adipic acid esters, fatty acid esters, glycols, epoxy polymer plasticizers, and the like can also be used.

  Examples of the oil include paraffinic process oil, naphthenic process oil, and isoparaffinic oil.

  Commercially available paraffinic process oils include “Diana Process Oil PW-32”, “Diana Process Oil PW-90”, “Diana Process Oil PW-150”, “Diana Process Oil PS-” manufactured by Idemitsu Kosan Co., Ltd. 32 ”,“ Diana Process Oil PS-90 ”,“ Diana Process Oil PS-430 ”;“ Kaydol Oil ”,“ ParaLux Oil ”manufactured by Chevron USA, etc. (all are trade names).

  Commercial products of isoparaffinic oil include “IP Solvent 1016”, “IP Solvent 1620”, “IP Solvent 2028”, “IP Solvent 2835”, “IP Clean LX” manufactured by Idemitsu Kosan Co., Ltd .; NOF Corporation ) “NA Solvent” series, etc. (all are trade names).

  Examples of the wax include animal wax, plant wax, carnauba wax, candelilla wax, wood wax, beeswax, mineral wax, petroleum wax, paraffin wax, microcrystalline wax, petrolatum, higher fatty acid wax, higher fatty acid ester wax, Fischer Examples include Tropsch wax.

  The content of the plasticizer (B) in the propylene-based resin composition of the present invention is 5 parts by mass or more with respect to 100 parts by mass of the resin (A), preferably from the viewpoint of improving adhesiveness and improving applicability. It is 10 parts by mass or more, more preferably 15 parts by mass or more, and 200 parts by mass or less, preferably 150 parts by mass or less, more preferably 100 parts by mass or less. From the viewpoint of improving applicability, the plasticizer (B) content is preferably low.

(Tackifier (C))
The propylene-based resin composition of the present invention may further contain a tackifier (C).
Examples of the tackifier include solid, semi-solid, or liquid materials at room temperature composed of hydrogenated derivatives of aliphatic hydrocarbon petroleum resins, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, and the like. be able to. Specifically, natural rosin, modified rosin, hydrogenated rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, pentaerythritol ester of hydrogenated rosin, natural Copolymers of terpenes, three-dimensional polymers of natural terpenes, hydrogenated derivatives of hydrogenated terpene copolymers, polyterpene resins, hydrogenated derivatives of phenolic modified terpene resins, aliphatic petroleum hydrocarbon resins, hydrogenation of aliphatic petroleum hydrocarbon resins Examples thereof include derivatives, aromatic petroleum hydrocarbon resins, hydrogenated derivatives of aromatic petroleum hydrocarbon resins, cycloaliphatic petroleum hydrocarbon resins, and hydrogenated derivatives of cycloaliphatic petroleum hydrocarbon resins. You may use these individually or in combination of 2 or more types. In the present invention, it is preferable to use a hydrogenated product in consideration of compatibility with the base polymer. Among them, a hydride of petroleum resin having excellent thermal stability is more preferable.

  Commercially available tackifiers include “Imabe” manufactured by Idemitsu Kosan Co., Ltd .; “Yumex” manufactured by Sanyo Chemical Industries, Ltd .; “Hilets” manufactured by Mitsui Chemicals, Inc .; manufactured by Yashara Chemical Co., Ltd. “Clearon”; “ECR” manufactured by Tonen Chemical Co., Ltd .; “Arcon” manufactured by Arakawa Chemical Co., Ltd .; “Regalrez”, “Eastotac”, “Regalite” manufactured by Eastman Chemical Co., Ltd .; manufactured by Nippon Zeon Co., Ltd. "Quinton"; "Escollets" manufactured by ExxonMobil; "Wingtac" manufactured by Clay Valley (all trade names).

  When the propylene-based resin composition of the present invention contains a tackifier (C), the content of the tackifier (C) in the propylene-based resin composition of the present invention is improved in tackiness, applicability, and reduced viscosity. From the viewpoint of improving the wettability of the adherend to the substrate, the resin (A) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 40 parts by mass or more, and still more preferably 100 parts by mass. It is 60 parts by mass or more, and preferably 500 parts by mass or less, more preferably 400 parts by mass or less, still more preferably 350 parts by mass or less, and still more preferably 200 parts by mass or less.

  Moreover, the content of the tackifier (C) in the propylene-based resin composition of the present invention varies depending on the type of the thermoplastic resin (A-2) from the viewpoint of adhesive strength.

  When the propylene resin composition of the present invention contains a styrene block copolymer or ethylene vinyl acetate copolymer as the thermoplastic resin (A-2), the tackifier (C in the propylene resin composition of the present invention) ) Content is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, and preferably 400 parts by mass or less with respect to 100 parts by mass of the resin (A). More preferably, it is 350 mass parts or less, More preferably, it is 300 mass parts or less.

  When the propylene resin composition of the present invention contains an ethylene olefin polymer or an amorphous polyolefin as the thermoplastic resin (A-2), the tackifier (C) in the propylene resin composition of the present invention is contained. The amount is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, still more preferably 40 parts by mass or more, and preferably 350 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the resin (A). Is 300 parts by mass or less, more preferably 250 parts by mass or less.

  When the propylene resin composition of the present invention contains a propylene elastomer as the thermoplastic resin (A-2), the content of the tackifier (C) in the propylene resin composition of the present invention is the resin (A). The amount is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more, and preferably 300 parts by mass or less, more preferably 250 parts by mass or less, further with respect to 100 parts by mass. Preferably it is 200 mass parts or less.

  The softening point of the tackifier (C) is not particularly limited, but from the viewpoint of controlling the glass transition point and elastic modulus of the hot melt adhesive to an appropriate range, the softening point of the tackifier (C). Is preferably −20 ° C. or higher, more preferably −15 ° C. or higher, further preferably −10 ° C. or higher, and preferably 180 ° C. or lower, more preferably 170 ° C. or lower, and further preferably 160 ° C. or lower. .

(Other additives)
The resin composition of the present invention may further contain an optional additive such as an inorganic filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, etc., as necessary, as long as the object of the present invention is not impaired. Good.

  Inorganic fillers include talc, calcium carbonate, barium carbonate, wollastonite, silica, clay, mica, kaolin, titanium oxide, diatomaceous earth, urea resin, styrene beads, starch, barium sulfate, calcium sulfate, magnesium silicate, Examples thereof include magnesium carbonate, alumina, and quartz powder.

  Antioxidants include trisnonyl phenyl phosphite, distearyl pentaerythritol diphosphite, “Adeka Stub 1178” (manufactured by ADEKA), “Stamilyzer TNP” (manufactured by Sumitomo Chemical Co., Ltd.), “Irgaphos 168” (Manufactured by BASF), “Sandstab P-EPQ” (manufactured by Sand), phosphorus antioxidants, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5 Phenolic antioxidants such as' -di-t-butyl-4'-hydroxyphenyl) propionate, "Smilizer BHT" (manufactured by Sumitomo Chemical Co., Ltd.), "Irganox 1010" (manufactured by BASF), dilauryl-3 , 3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), Examples include sulfur antioxidants such as "Sumilyzer TPL" (manufactured by Sumitomo Chemical Co., Ltd.), "DLTP" Yoshitomi "(manufactured by Mitsubishi Chemical Corporation), and" Antiox L "(manufactured by NOF Corporation). .

(Producing method of propylene resin composition)
The propylene resin composition of the present invention is obtained by dry blending the above resin (A) and plasticizer (B), and further, if necessary, a tackifier (C) and additives using a Henschel mixer or the like. It can be produced by melt-kneading with a shaft or twin screw extruder, a plast mill, a Banbury mixer or the like.

[Hot melt adhesive]
The hot melt adhesive of the present invention contains the propylene polymer (A-1) or the propylene resin composition.

(1) Tensile Breaking Elongation of Hot Melt Adhesive From the viewpoint of making the hot melt adhesive less susceptible to cohesive failure, the tensile breaking elongation at 23 ° C. of the hot melt adhesive is preferably 150% or more, more preferably 190% or more. More preferably, it is 210% or more, and still more preferably 240% or more. The tensile elongation at break is measured by the method described in the examples.

(2) Tensile rupture strength of hot melt adhesive From the viewpoint of adhesive strength of hot melt adhesive, the tensile rupture strength of hot melt adhesive at 23 ° C is preferably 4 MPa or more, more preferably 4.5 MPa or more, and still more preferably. Is 6.5 MPa or more, more preferably 8 MPa or more. The tensile elongation at break is measured by the method described in the examples.

  The tensile elongation at break and the tensile strength at break of the hot melt adhesive vary the polymerization conditions (reaction temperature, reaction time, catalyst, promoter) of the propylene polymer (A-1), or are thermoplastic resins (A-2). ), And by varying the components and blending amounts of the plasticizer (B) and the tackifier (C), it can be adjusted within a desired range. Moreover, the tensile breaking elongation and tensile breaking strength of a hot-melt adhesive agent can be made high by increasing the compounding quantity of a thermoplastic resin (A-2).

(3) Shore D hardness of hot melt adhesive From the viewpoint of improving the interfacial adhesive strength of the hot melt adhesive, it is preferable that the hot melt adhesive is soft to some extent. The Shore D hardness of the hot melt adhesive measured according to ASTM D2240 is preferably 10 or less, more preferably 7.5 or less, still more preferably 6.5 or less, and even more preferably 5 or less.
The Shore D hardness of the hot melt adhesive can be lowered by increasing the blending amount of the thermoplastic resin (A-2).

(4) Melt viscosity of hot melt adhesive (B type viscosity)
From the viewpoint of the balance between fluidity and handleability of the hot melt adhesive, the melt viscosity of the hot melt adhesive measured with a B-type viscometer at 190 ° C. is preferably 2,000 mPa · s or more, more preferably 2, 500 mPa · s or more, more preferably 3,000 mPa · s or more, and preferably 6,000 mPa · s or less, more preferably 5,800 mPa · s or less, and further preferably 5,700 mPa · s or less. The B-type viscosity of the hot melt adhesive is measured by the method described in the examples.

  The tensile elongation at break, tensile strength at break and Shore D hardness of the hot melt adhesive can be improved by increasing the amount of the thermoplastic resin (A-2), but the B-type viscosity of the hot melt adhesive is When the blending amount of the thermoplastic resin (A-2) is increased, the thermoplastic resin (A-2) is drastically lowered and adversely affects the fluidity of the hot melt adhesive. On the other hand, since the hot melt adhesive of the present invention uses a relatively low viscosity propylene polymer (A-1) as the base polymer, the amount of the thermoplastic resin (A-2) is increased. However, the interfacial adhesive strength is improved while maintaining or improving the fluidity, and the tensile fracture strength is increased, so that the material fracture is suppressed, and the adhesive strength can be improved from the side surface.

  The hot melt adhesive of the present invention uses a propylene-based polymer (A-1) having a relatively low viscosity as a base polymer, and therefore has excellent fluidity and low-temperature coating properties, and is particularly suitable for spray coating as a coating method. Can do.

  In addition, the hot melt adhesive of the present invention is excellent in adhesiveness with various substrates containing low polar substances such as polyolefins, and is excellent in thermal stability at the time of heating and melting. It can be suitably used for packaging, bookbinding, textiles, woodworking, electrical materials, can making, construction, filtering, low pressure molding and bag making.

  Particularly suitable for the adhesion of polyolefin-based materials, and because it uses a base polymer containing both a high modulus component and a low modulus component, it exhibits a well-balanced adhesion. It is used for adhesion between nonwoven fabrics, adhesion between polyolefin film and polyolefin nonwoven fabric, and preferably used for adhesion between PP nonwoven fabric and PP nonwoven fabric, and adhesion between PE film and PP nonwoven fabric. For this reason, sanitary products such as disposable diapers and sanitary products containing the hot melt adhesive of the present invention are suitable.

  The propylene-based polymer (A-1) of the present invention can be used as an adhesive exhibiting sufficient adhesiveness as a simple substance, even if it does not contain a plasticizer and a tackifier depending on the type of adherend. . For example, it can be preferably used as an adhesive applied to business applications such as assembly applications typified by automobile floor mats and sanitary material applications typified by fixing nonwoven fabrics or superabsorbent polymers (SAP). The main reasons that can be used for these applications are as follows. First, when the adherend has sufficient unevenness, the propylene polymer (A-1) of the present invention alone can exhibit a sufficient anchor effect. Secondly, the above application does not require a strong adhesive force in the first place, and it is not necessary to add a plasticizer and a tackifier for improving adhesiveness. Thirdly, in the above applications, the generation of odors and volatile components derived from plasticizers and tackifiers is undesirable, and the propylene polymer (A-1) of the present invention which does not generate odors and volatile components alone is used. Is preferred.

  Incidentally, the propylene polymer having a molecular weight higher than that of the propylene polymer (A-1) of the present invention does not include a plasticizer and a tackifier depending on the kind of the adherend, like the propylene polymer of the present invention. Both of them can be used as an adhesive exhibiting sufficient adhesiveness as a simple substance, and can be used for assembly applications such as automobile floor mats, and hygiene such as non-woven fabric or superabsorbent polymer (SAP) fixation. It can be preferably used as an adhesive applied to business use such as material use.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

[Viscosity measurement with B-type viscometer]
Based on ASTM D3236, it was measured at 190 ° C. using a Brookfield rotational viscometer.

[DSC measurement]
Using a differential scanning calorimeter (Perkin Elmer, “DSC-7”), 10 mg of the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. It calculated | required as a melting endotherm ((DELTA) HD) from a melting endothermic curve. Moreover, melting | fusing point (Tm-D) was calculated | required from the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve.
The melting endotherm (ΔH-D) is a differential scanning calorimeter (manufactured by Perkin Elmer Co., Ltd.) with a line connecting a point on the low temperature side where there is no change in heat quantity and a point on the high temperature side where there is no change in heat quantity as the baseline , “DSC-7”), and calculating the area surrounded by the line portion including the peak of the melting endothermic curve obtained by DSC measurement and the base line.

[NMR measurement]
The ¹³ C-NMR spectrum was measured using the following apparatus and conditions. In addition, the attribution of the peak followed the method proposed by A. Zambelli et al. In “Macromolecules, 8, 687 (1975)”.
Apparatus: “JNM-EX400 type ¹³ C-NMR apparatus” manufactured by JEOL Ltd.
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

<Calculation 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: 21.7-22.5 ppm

The mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic mesoracemi mesopentad fraction [rmrm] are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. The meso fraction, the racemic fraction, and the racemic meso-racemic meso in the pentad unit in the polypropylene molecular chain measured by the methyl group signal in the ¹³ C-NMR spectrum were obtained according to the proposed method. It is a fraction. As the mesopentad fraction [mmmm] increases, the stereoregularity increases. The triad fractions [mm], [rr] and [mr] were also calculated by the above method.

Furthermore, from the measurement results of the ¹³ C-NMR spectrum, a 1,3-bond fraction and a 2,1-bond fraction were calculated by the following formulas.
1,3-bond fraction = (D / 2) / (A + B + C + D) × 100 (mol%)
2,1-bond fraction = [(A + B) / 2] / (A + B + C + D) × 100 (mol%)
A: integrated value of 15 to 15.5 ppm B: integrated value of 17 to 18 ppm C: integrated value of 19.5 to 22.5 ppm D: integrated value of 27.6 to 27.8 ppm

[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) measurement]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method to determine the molecular weight distribution (Mw / Mn). For the measurement, the following equipment and conditions were used, and polystyrene-reduced weight average molecular weight and number average molecular weight were obtained. The molecular weight distribution (Mw / Mn) is a value calculated from these weight average molecular weight (Mw) and number average molecular weight (Mn).
<GPC measurement 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)

Production Example 1
(Production of propylene polymer (A-1a))
To a stainless steel reactor with an internal volume of 20 L equipped with a stirrer, 20 mL / hr of n-heptane, 15 mmol / hr of triisobutylaluminum, dimethylanilinium tetrakis (pentafluorophenyl) borate, (1,2′-dimethyl) A catalyst component obtained by previously contacting silylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride and triisobutylaluminum in a mass ratio of 1: 2: 20 in advance with propylene, It was continuously supplied at 6 μmol / hr in terms of zirconium.
A polymerization solution having a desired molecular weight, maintaining the total pressure in the reactor at 1.0 MPa · G, continuously supplying hydrogen and propylene so that the hydrogen / propylene ratio is 0.16, setting the polymerization temperature to 87 ° C. Got. The propylene polymer (A-1a) was obtained by adding antioxidant to the obtained polymerization solution so that the content rate might become 1000 mass ppm, and then removing n-heptane which is a solvent.

Production Example 2
(Production of propylene polymer (A-1b))
Propylene polymer (A-1b) was obtained in the same manner as in Production Example 1, except that hydrogen and propylene were continuously supplied so that the hydrogen / propylene ratio was 0.35, and the polymerization temperature was 75 ° C. .

  The above measurements were performed on the propylene polymers (A-1a) and (A-1b) obtained in Production Examples 1 and 2. The results are shown in Table 1.

Example 1 and Comparative Example 1
(Manufacture of hot melt adhesive)
After putting the materials described in Table 2 into a sample bottle at a blending ratio (mass ratio) described in Table 2 so that the B-type viscosity is 5,000 mPa · s, and heating and melting at 180 ° C. for 30 minutes, Thorough mixing and stirring were performed with a rotary blade to produce hot melt adhesives. The obtained hot melt adhesive was evaluated as follows.

In addition, the raw material used by the Example and the comparative example is as follows.
<Thermoplastic resin (A-2)>
Styrene-Butadiene-Styrene Thermoplastic Elastomer (SBS) ("ASAPRENE T-439", manufactured by Asahi Kasei Corporation)
<Plasticizer (B)>
Paraffin process oil ("Diana Process Oil PW-90", manufactured by Idemitsu Kosan Co., Ltd.)
<Tackifier (C)>
Hydrogenated derivatives of aliphatic hydrocarbon petroleum resins (“Escollets 5400”, manufactured by Tonen Chemical Co., Ltd., softening point 100 ° C.)

[Viscosity measurement with B-type viscometer]
Based on ASTM D3236, it was measured at 190 ° C. using a Brookfield rotational viscometer.

[Shore D hardness]
A 3 mm thick sheet was produced by a press molding machine and allowed to elapse for 48 hours at room temperature after measurement, and then the scale was read immediately after contact with the pressing needle using an A-type measuring instrument (according to ASTM D2240).

(Measurement of tensile strength and tensile elongation)
Based on JIS K7113, the tensile breaking strength and the tensile breaking elongation were measured under the following conditions.
-Test piece: JIS K7113-1 / 2 size dumbbell (thickness: 1 mm)
・ Measurement temperature: 23 ℃
・ Tensile speed: 100 mm / min ・ Distance between chucks: 40 mm

  From the comparison between Example 1 and Comparative Example 1 matched to the same viscosity, compared to the hot melt adhesive of Comparative Example 1, the hot melt adhesive of Example 1 has a lower Shore D hardness at the same viscosity and a tensile fracture. High strength. Here, the lower the Shore D hardness, the softer the adhesive surface and the better the interfacial adhesive strength. Also, the difference in tensile rupture strength is 1 MPa, which appears to be a slight difference, but raising 6 MPa by 1 MPa is a remarkable difference because the improvement rate is about 17%. Therefore, the hot melt adhesive according to one aspect of the present disclosure can increase the amount of the high molecular weight resin, maintain fluidity, improve interfacial adhesive strength, and increase tensile rupture strength. Material destruction is suppressed, and the adhesive strength is also improved from the side.

Examples 2 and 3
A hot melt adhesive was produced and evaluated in the same manner as in Example 1 except that the blending ratio (mass ratio) of the materials was changed as shown in Table 3.

  As can be seen from the results of Example 2, the propylene-based polymer of one embodiment of the present disclosure has a low viscosity and can improve fluidity and interfacial adhesive strength. In addition, as can be seen from the results of Example 3, the hot melt adhesive according to one aspect of the present disclosure can suppress a decrease in fluidity even when the blending amount of the high molecular weight resin is increased. The tensile strength at break can be greatly improved, and the adhesive strength can be improved.

  The hot melt adhesive containing the resin composition of the present invention can improve adhesive strength while maintaining or improving fluidity. Therefore, the hot melt adhesive of the present invention is an adhesive for sanitary goods such as pant-type diapers, woodworking, packaging, bookbinding, textiles, electrical materials, cans, buildings and bags. It can be suitably used as an adhesive.

Claims (14)

  The melting endotherm (ΔH-D) measured with a differential scanning calorimeter (DSC) is 0 to 80 J / g, and the viscosity measured with a B-type viscometer at 190 ° C. is 500 to 6,000 mPa · s. A certain propylene polymer. The propylene-based polymer according to claim 1, which satisfies at least one of the following (i) and (ii).
(I) The structural unit of ethylene is contained in an amount exceeding 0 mol% and not more than 35 mol%.
(Ii) The structural unit of 1-butene is contained in an amount of more than 0 mol% and 45 mol% or less. The propylene polymer according to claim 1 or 2, which satisfies the following (1).
(1) Mesopentad fraction [mmmm] is 20 mol% or more and 80 mol% or less. The propylene-based polymer according to any one of claims 1 to 3, which satisfies the following (2).
(2) The value of [rrrr] / (1- [mmmm]) is 0.1 or less. A propylene-based resin composition containing a resin (A) and a plasticizer (B),
The said resin (A) contains the propylene-type polymer (A-1) as described in any one of Claims 1-4, and content of the said plasticizer (B) is the said resin (A) 100 mass. The propylene-type resin composition which is 5-200 mass parts with respect to a part.   The propylene-based resin composition according to claim 5, wherein the plasticizer (B) is oil or wax.   The tackifier (C) is further contained, and the content of the tackifier (C) is 10 to 500 parts by mass with respect to 100 parts by mass of the resin (A). Propylene-based resin composition.   The propylene-type resin composition of Claim 7 whose softening point of the said tackifier (C) is -20-180 degreeC. The resin (A) includes the propylene polymer (A-1) and a thermoplastic resin (A-2) other than the propylene polymer (A-1),
The mass ratio ((A-1) / (A-2)) between the propylene polymer (A-1) and the thermoplastic resin (A-2) is 5/95 to 99/1. The propylene-based resin composition according to any one of 5 to 8.   The thermoplastic resin (A-2) contains at least one selected from the group consisting of a styrene block copolymer, an ethylene vinyl acetate copolymer, an ethylene olefin polymer, an amorphous polyolefin, and a propylene elastomer. The propylene-based resin composition according to claim 9.   The thermoplastic resin (A-2) contains a styrene block copolymer or an ethylene vinyl acetate copolymer, and the content of the tackifier (C) is 40 parts by mass with respect to 100 parts by mass of the resin (A). The propylene-type resin composition of Claim 10 which is -400 mass parts.   The thermoplastic resin (A-2) contains an ethylene-based olefin polymer or an amorphous polyolefin, and the content of the tackifier (C) is 30 to 350 masses with respect to 100 mass parts of the resin (A). The propylene-based resin composition according to claim 10, which is a part.   The thermoplastic resin (A-2) includes a propylene-based elastomer, and the content of the tackifier (C) is 10 to 300 parts by mass with respect to 100 parts by mass of the resin (A). The propylene-based resin composition described in 1.   The hot-melt-adhesive containing the propylene-type polymer as described in any one of Claims 1-4, or the propylene-type resin composition as described in any one of Claims 5-13.