JP7044557B2 - Butene-based resin composition and molded product - Google Patents

Description

The present invention relates to a butene-based resin composition containing a butene / α-olefin copolymer and a molded product composed of the above composition.

Pipes, pipe joints and tanks made of butene polymers are excellent in creep resistance, environmental stress crack resistance, flexibility, toughness, heat resistance, high temperature / low temperature characteristics and wear resistance, so that water can be supplied. -It is used as various materials for hot water supply, underfloor heating, hot spring piping, chemical spraying, drainage, etc.

There are mainly two types of crystal types in the butene-based polymer, and immediately after the butene-based polymer is cooled and shaped into a molded body from a molten state, it has a semi-stable type II crystal structure (tetragonal transformation). It is known that a solid-phase crystal transition to a more stable type I crystal structure (tetragonal transformation) takes about one week (Non-Patent Document 1).

The butene-based polymer has a drawback that the crystal transition causes a change in size and rigidity after molding, and the crystal transition time is long, which complicates quality control and inventory control by the customer. That is, in the technical field of melt molding a butene-based polymer, a polymer having a short crystal transition time from a type II crystal to a type I crystal is required.

In response to this requirement, a method of blending a radically treated crystalline olefin polymer with a butene polymer (see Patent Document 1) and adding an additive to the butene polymer for the purpose of shortening the crystal transition time. (See Patent Documents 2 and 3) and a method of introducing a comonomer (see Patent Document 4) are known.

On the other hand, Patent Document 5 discloses a polybutene-based resin obtained by mixing two kinds of polybutene-based resins having a high isotactic index (for example, 1-butene-propylene copolymer and 1-butene homopolymer). ing. Further, Patent Documents 6 and 7 disclose 1-butene polymers having high stereoregularity.

Japanese Unexamined Patent Publication No. 61-037833 Japanese Unexamined Patent Publication No. 57-036140 Japanese Unexamined Patent Publication No. 57-092038 Japanese Unexamined Patent Publication No. 2016-147983 Japanese Unexamined Patent Publication No. 2002-256024 International Publication No. 2014/050817 International Publication No. 2017/130895

Journal of Polymer Science: PartA volume1 page59-84 (1963)

In the butene-based polymer, further improvement is required for the effect of shortening the molding cost and the crystal transition time into pipes, pipe joints, tanks and the like. As described above, a method of introducing a comonomer into a butene-based polymer can be adopted in order to shorten the crystal transition time, but the introduction of the comonomer lowers the crystallinity of the polymer. There is concern that the mechanical properties will deteriorate due to the decrease in crystallinity. It is desirable that the introduction of comonomers shortens the crystal transition time while suppressing the decrease in crystallinity and does not decrease the mechanical properties and long-term physical properties.

An object of the present invention is a butene-based copolymer having a short crystal transition time from a type II crystal to a type I crystal as a main component, and a butene having a small possibility of deterioration of mechanical properties by suppressing a decrease in crystallinity. The present invention is to provide a based resin composition.

The present inventors have made diligent studies to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by adding a 1-butene homopolymer having high stereoregularity to the base butene-based copolymer, and have completed the present invention.

The present invention relates to the following [1] to [3].
[1]
70 to 99.9 parts by mass of a butene / α-olefin copolymer (A) satisfying the following requirements (A1) to (A2), and polybutene-1 (B) satisfying the following requirements (B1) to (B4). A butene-based resin composition containing 0.1 to 30 parts by mass (however, the total of the butene / α-olefin copolymer (A) and polybutene-1 (B) is 100 parts by mass).
(A1): At least one selected from ethylene and α-olefins other than 1-butene having 3 to 20 carbon atoms and having a content of 1-butene-derived structural units of 80.0 to 99.9 mol%. The total content (K) of the constituent units derived from olefin is 0.1 to 20.0 mol%. (However, the total of the content of the constituent unit derived from 1-butene and the total content (K) is 100 mol%).
(A2): The ultimate viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.5 dl / g.
(B1): ¹³ The isotactic pentad fraction measured by C-NMR is 94.0% or more.
(B2): ¹³ The syndiotactic triad fraction measured by C-NMR is 1.5% or less.
(B3): The ultimate viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.5 dl / g.
(B4): The proportion of components having a molecular weight of 10,000 or less as measured by gel permeation chromatography (GPC) is less than 1.3% by mass.

[2]
A molded product made of the butene-based resin composition of the above [1].
[3]
The molded body of the above [2] which is a pipe or a pipe joint.

The butene-based resin composition of the present invention is mainly composed of a butene-based copolymer having a short crystal transition time from a type II crystal to a type I crystal, and has mechanical properties due to the suppression of a decrease in crystallinity. There is little risk of deterioration.

FIG. 1 is a plot of the heat of fusion ΔH with respect to the ratio of polybutene-1 in the butene-based resin compositions of Examples and Comparative Examples. FIG. 2 is a plot of the semi-crystallization time at a crystallization temperature of 85 ° C. with respect to the ratio of polybutene-1 in the butene-based resin compositions of Examples and Comparative Examples.

The present invention will be described in more detail.
[Butene resin composition]
The butene-based resin composition according to the present invention contains 70 to 99.9 parts by mass of a butene / α-olefin copolymer (A) satisfying the requirements (A1) to (A2) described later, and the requirement (B1) described later. 0.1 to 30 parts by mass of polybutene-1 (B) satisfying (B4) (however, the total of butene / α-olefin copolymer (A) and polybutene-1 (B) is 100 parts by mass). Includes.

Hereinafter, the 1-butene homopolymer and the butene-based copolymer may be referred to as "butene-based polymer" without particular distinction.
[(A) Butene / α-olefin copolymer]
The butene / α-olefin copolymer (A) satisfies the requirements (A1) to (A2) described below, and is preferably selected from the group consisting of the requirements (A3) to (A4) described below. At least one requirement is further satisfied, and more preferably the requirements (A3) and (A4) described below are satisfied.

<< Requirements (A1) >>
The requirement (A1) is that the content of 1-butene-derived structural units is 80.0 to 99.9 mol%, and at least one selected from ethylene and α-olefins other than 1-butene having 3 to 20 carbon atoms. The total content (K) of the constituent units derived from the seed olefin is 0.1 to 20.0 mol% (however, the total content of the constituent units derived from 1-butene and the total content (K). Is 100 mol%.).

In the present specification, "ethylene" and "α-olefin other than 1-butene having 3 to 20 carbon atoms" are also referred to as "comonomer". The total content (K) is the total content of the constituent units (comonomer units) derived from the comonomer. When the butene / α-olefin copolymer (A) contains a structural unit derived from a comonomer, the structural unit may be a structural unit derived from one type of comonomer, or a configuration derived from two or more types of comonomer. It may be a unit.

In the butene / α-olefin copolymer (A), the content of the structural unit derived from 1-butene is 85.0 to 99.9 mol%, and the total content (K) is 0.1 to. The content is preferably 15.0 mol%, the content of the constituent unit derived from 1-butene is 90.0 to 99.9 mol%, and the total content (K) is 0.1 to 10.0 mol. % Is more preferable. The content of the structural unit derived from 1-butene is 90.0 to 96.5 mol%, and the total content (K) is more preferably 3.5 to 10.0 mol%, more preferably 1-butene. It is particularly preferable that the content of the derived constituent unit is 93.2 to 96.1 mol% and the total content (K) is 3.9 to 6.8 mol%.

When the content of the structural unit derived from 1-butene and the total content (K) are in the above range, the crystal transition time of the butene / α-olefin copolymer (A) is short, and the butene system of the present invention is obtained. The effect of shortening the crystal transition time of the resin composition and the mechanical properties of the butene-based resin composition are excellent in a well-balanced manner.

The content of the constituent units derived from the comonomer described above is measured by ¹³ C-NMR under the conditions adopted in the examples described later.
The content of each structural unit in the butene / α-olefin copolymer (A) is, for example, the content of each olefin added during the polymerization reaction (eg, 1-butene, ethylene, 1-with 3 to 20 carbon atoms). It can be adjusted by the amount of α-olefin (α-olefin other than butene).

Examples of α-olefins other than 1-butene having 3 to 20 carbon atoms include propylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, and 3-ethyl-1. -Pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Among these, propylene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene preferable.

Among the comonomer, ethylene and α-olefin having 3 to 10 carbon atoms are more preferable, ethylene and propylene are preferable, and propylene is particularly preferable. Propylene has a similar crystal spiral structure to 1-butene, so that the crystal transition time can be shortened.

The comonomer may be used alone or in combination of two or more.
The butene-α-olefin copolymer (A) has a structural unit derived from other monomers other than ethylene and α-olefin having 3 to 20 carbon atoms, as long as the effect of the present invention is not impaired. May be good. The upper limit of the content of the constituent units derived from other monomers is, for example, 5 mass or less with respect to the total content of 100 mass% of the content of the constituent units derived from 1-butene and the total content (K). ..

<< Requirements (A2) >>
The requirement (A2) is that the ultimate viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.5 dl / g.

The ultimate viscosity [η] is preferably 0.7 to 5.0 dl / g, more preferably 0.7 to 4.5 dl / g, still more preferably 0.7 to 4.0 dl / g, and particularly preferably 0. It is 0.7 to 2.8 dl / g.

When the ultimate viscosity [η] is at least the lower limit value, the strength of the molded product obtained from the butene-based resin composition of the present invention is excellent. When the ultimate viscosity [η] is not more than the upper limit value, the butene-based resin composition of the present invention is excellent in moldability, and is advantageous in terms of shortening of crystal transition time or flexibility.

The ultimate viscosity [η] can be adjusted by adjusting the hydrogen concentration and pressure of the polymerization system during the production of the butene / α-olefin copolymer (A), and the butene / α- having a different ultimate viscosity [η] can be adjusted. The olefin copolymers (A) may be mixed and adjusted.

<< Requirements (A3) >>
The requirement (A3) is that the isotactic pentad fraction (hereinafter also referred to as "mmmm fraction") measured by ¹³ C-NMR under the conditions adopted in the examples described later is 90.0% or more 94. It is said to be 0.0% or less.

When the mmmm fraction is at least the lower limit, the crystallization rate of the butene / α-olefin copolymer (A) is high, and the crystallization of the butene-based resin composition of the present invention is promoted. The mmmm fraction can be adjusted within the above range by appropriately selecting a polymerization catalyst for polymerizing the butene / α-olefin copolymer (A) and setting polymerization conditions such as the polymerization temperature. can.

<< Requirements (A4) >>
The requirement (A4) is that the syndiotactic triad fraction (hereinafter, also referred to as "rr fraction") measured by ¹³ C-NMR under the conditions adopted in the examples described later is 1.5% or more. It is 0% or less.

When the rr is not more than the upper limit value, the crystallization rate of the butene / α-olefin copolymer (A) is high, and the crystallization of the butene-based resin composition of the present invention is promoted. The rr can be adjusted within the above range by appropriately selecting a polymerization catalyst for polymerizing the butene / α-olefin copolymer (A) and appropriately setting the polymerization conditions such as the polymerization temperature.
The rr fraction can be adjusted by selecting a polymerization catalyst when polymerizing the butene / α-olefin copolymer (A), adjusting the polymerization conditions such as the polymerization temperature, and the like.

(Method for producing butene / α-olefin copolymer (A))
The butene-α-olefin copolymer (A) may be a conventionally known catalyst, for example, a vanadium-based catalyst, a titanium-based catalyst, a magnesium-supported titanium catalyst, or International Publication No. 01/53369, International Publication No. 01/27124. It can be produced by a conventionally known polymerization method using the metallocene catalyst described in No. 3 or Japanese Patent Application Laid-Open No. 3-193996.

[(B) Polybutene-1]
The butene-based resin composition according to the present invention contains polybutene-1 (1-butene homopolymer) (B). Polybutene-1 (B) satisfies the requirements (B1) to (B4) described below.

<< Requirements (B1) >>
The requirement (B1) is that the isotactic pentad fraction (mmmm fraction) measured by ¹³ C-NMR under the conditions adopted in the examples described later is 94.0% or more.

The mmmm fraction is preferably 94.0 to 99.5%, more preferably 95.0 to 99.5%, even more preferably 95.0 to 99.0%, and particularly preferably 95.0% to. It is 98.5%, particularly preferably 95.0% to 98.0%.

When the mmmm fraction is at least the lower limit value, the crystallization rate of the polybutene-1 (B) is high, and the crystallization of the butene-based resin composition of the present invention is promoted.
The mmmm fraction can be adjusted within the above range by appropriately selecting a polymerization catalyst for polymerizing polybutene-1 (B) and setting polymerization conditions such as polymerization temperature.

<< Requirements (B2) >>
The requirement (B2) is that the syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR under the conditions adopted in the examples described later is 1.5% or less.

The rr fraction is preferably 1.3% or less, more preferably 1.1% or less, even more preferably 1.0% or less, particularly preferably 0.8% or less, still more preferably 0. It is 5% or less, particularly preferably 0.4% or less. The lower the rr fraction is, the more preferable, but the lower limit thereof may be, for example, 0.01%.

When the rr fraction is not more than the upper limit value, the crystallization rate of the polybutene-1 (B) is high, and the crystallization of the butene-based resin composition of the present invention is promoted.
The rr fraction can be adjusted within the above range by appropriately selecting a polymerization catalyst for polymerizing polybutene-1 (B) and appropriately setting polymerization conditions such as polymerization temperature.

<< Requirements (B3) >>
The requirement (B3) is that the ultimate viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.5 dl / g.
The ultimate viscosity [η] is preferably 0.7 to 5.0 dl / g, more preferably 0.7 to 4.5 dl / g, still more preferably 0.7 to 4.0 dl / g, and particularly preferably 0. It is 0.7 to 2.8 dl / g.

When the ultimate viscosity [η] is at least the lower limit value, the strength of the molded product obtained from the butene-based resin composition of the present invention is excellent. When the ultimate viscosity [η] is not more than the upper limit value, the butene-based resin composition of the present invention is excellent in moldability, and is advantageous in terms of shortening of crystal transition time or flexibility.

The ultimate viscosity [η] can be adjusted by adjusting the hydrogen concentration and pressure of the polymerization system during the production of polybutene-1 (B), and the polybutene-1 having different extreme viscosities [η] can be mixed and adjusted. You may.

<< Requirements (B4) >>
The requirement (B4) is that the proportion of the component of polybutene-1 (B) having a molecular weight of 10,000 or less as measured by gel permeation chromatography (GPC; standard polystyrene equivalent) is less than 1.3% by mass. That is. This ratio is preferably 0.9% by mass or less. The lower limit may be, for example, 0.1% by mass.

When the ratio of the components having a molecular weight of 10,000 or less is within the above range, there are few low molecular weight components that may impair the creep strength of the molded product. Therefore, the butene-based resin composition according to the present invention has creep resistance. A molded body having excellent characteristics can be obtained.
The ratio of the components having a molecular weight of 10,000 or less can be adjusted within the above range by appropriately selecting a polymerization catalyst for polymerizing polybutene-1 (B).

(Manufacturing method of polybutene-1 (B))
The polybutene-1 (B) is produced by using only 1-butene as a raw material monomer in a conventionally known method, for example, the method disclosed in International Publication No. 2017/130895 [0059] to [0144]. can do.

[Butene-based resin composition]
The butene-based resin composition according to the present invention contains 70 to 99.9 parts by mass of the butene / α-olefin copolymer (A) and 0.1 to 30 parts by mass of the polybutene-1 (B). , Butene / α-olefin copolymer (A) and polybutene-1 (B) total 100 parts by mass).

The butene-based resin composition according to the present invention preferably contains 75 to 99 parts by mass of the butene / α-olefin copolymer (A) and 1 to 25 parts by mass of the polybutene-1 (B), more preferably. It contains 75 to 95 parts by mass of the butene / α-olefin copolymer (A) and 5 to 25 parts by mass of the polybutene-1 (B) (however, the butene / α-olefin copolymer (A) and the polybutene-. 1 (B) is 100 parts by mass).

Since the butene-based resin composition according to the present invention contains the polybutene-1 (B) in the above ratio, the crystal transition time is short and the crystallinity is high.
As a method for evaluating the crystallinity of the butene-based resin composition of the present invention, for example, there is a method of comparing the amount of heat of fusion ΔH between samples. ΔH is determined by differential scanning calorimetry (heating rate: 10 ° C./min).

The heat of fusion ΔH of the butene-based resin composition is measured under the following conditions. The butene-based resin composition was heated from 30 ° C. to 200 ° C. at a heating rate of 500 ° C./min using a differential scanning calorimeter (DSC), held at 200 ° C. for 5 minutes, and then further 10 ° C./. The temperature is lowered to 30 ° C. at a cooling rate of 30 ° C., held at 30 ° C. for 5 minutes, and then raised again from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min. Here, the melting peak that appears at the time of the second temperature rise is known as the melting point TmII derived from the type II crystal. The amount of heat of melting based on the melting peak of this type II crystal is evaluated as the amount of heat of melting ΔH of the butene-based resin composition.

As a method for evaluating the crystallization rate of the butene resin composition of the present invention, for example, there is a method for evaluating the sample semi-crystallization time τ _1/2 . The semi-crystallization time τ _1/2 is determined by differential scanning calorimetry.

The semi-crystallization time τ _1/2 of the butene-based resin composition is measured under the following conditions. The butene-based resin composition is heated from 30 ° C. to 200 ° C. at a set rate of 320 ° C./min using a differential scanning calorimeter (DSC), held for 10 minutes, and then lowered to a predetermined crystallization temperature. The temperature is lowered at a set rate of 320 ° C./min, and the crystallization peak under isothermal temperature is measured. From the measured crystallization peak, the time from the time when crystallization started to the time when crystallization is half accelerated (when the area becomes 1/2 of the total crystallization peak area) is τ _1/2 . Measure as. It can be said that the shorter the τ _1/2 , the faster the crystallization rate.

In the present invention, the heat of fusion ΔH and the melting point TmII of the butene-based resin composition are constituent units derived from 1-butene of the butene / α-olefin copolymer (A) in addition to increasing the proportion of polybutene-1 (B). It is increased by increasing the content of, or selecting an appropriate olefin-based catalyst to increase mmmm (%) and decrease rr (%).

The butene-based resin composition of the present invention has a heat of melting by blending a butene / α-olefin copolymer (A) with polybutene-1 (B) having a high mm mm (%) and a low rr (%). The heat of melting ΔH is shown to be a value higher than the value derived from the straight line connecting the heats of melting ΔH of both simplexes because the addability for ΔH does not hold. That is, the crystallinity is high.

Analysis of τ _1/2 shows that polybutene-1 (B) with high mmmm (%) and low rr (%) has short τ _1/2 , low mmmm (%) and low rr (%). Higher crystallization rate compared to high butene homopolymers or butene-based copolymers. When polybutene-1 (B) having a high mmmm (%) and a low rr (%) is blended with the butene / α-olefin copolymer (A), τ ₁ of the butene / α-olefin copolymer (A) is obtained. _{/ 2} becomes shorter. That is, the crystallization rate is increased. It is considered that polybutene-1 (B) promotes the crystallization of the butene / α-olefin copolymer (A) and the crystallinity is increased.

(Arbitrary components of butene-based resin composition, etc.)
The butene-based resin composition of the present invention contains the above-mentioned butene-α-olefin copolymer (A) and polybutene-1 (B).

The butene-based resin composition of the present invention may optionally contain at least one selected from other polymers and additives for resins, depending on its use, as long as the effects of the present invention are not impaired. Hereinafter, polymers other than the butene / α-olefin copolymer (A) and polybutene-1 (B) are also referred to as “other polymers (C)”, and the resin additive is also referred to as “additive (D)”. say.

The butene-based resin composition of the present invention may be partially or wholly graft-modified with a polar monomer. The details of graft denaturation will be described later in the column of << Graft denaturation >>.

<< Butene / α-olefin copolymer (A) and polybutene-1 (B) >>
The total content of the butene / α-olefin copolymer (A) and polybutene-1 (B) is 0.1 to 99.99% by mass with respect to the total mass of the butene-based resin composition of the present invention. The lower limit is preferably 20% by mass, and in one embodiment, the lower limit of the content of the butene / α-olefin copolymer (A) is, for example, 40% by mass, more preferably 60% by mass. %, Especially preferably 80% by mass, and most preferably 85% by mass.

A part or all of the butene / α-olefin copolymer (A) may be graft-modified with a polar monomer as long as the above requirements are satisfied. The details of graft denaturation will be described later in the column of << Graft denaturation >>.

<< Other polymer (C) >>
As the other polymer (C), a thermoplastic resin can be widely used. The content of the other polymer (C) is preferably 0.001 to 99.9% by mass, and the upper limit is preferably 80% by mass, based on the total mass of the butene-based resin composition of the present invention. In one embodiment, the upper limit of the content of the other polymer (C) is more preferably 60% by mass, further preferably 40% by mass, particularly preferably 20% by mass, and most preferably 15% by mass. Is.

The thermoplastic resin is not particularly limited, but is not particularly limited.
Thermoplastic polyolefin-based resins: For example, low-density, medium-density, high-density polyethylene, polyethylene such as high-pressure low-density polyethylene, isotactic polypropylene, polypropylene such as syndiotactic polypropylene, and poly 1 other than polybutene-1 (B). -Buten, poly4-methyl-1-pentene, poly3-methyl-1-pentene, poly3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1- Butene / α-olefin copolymer, 4-methyl-1-pentene / α-olefin copolymer, cyclic olefin copolymer, chlorinated polyolefin, and modified polyolefin resin obtained by modifying these olefin-based resins (heat described above). Among the plastic polyolefin-based resins, for example, polyethylene and polypropylene can also be used as the crystal nucleating agent, and the preferable content in that case is 0.001 to 5% by mass with respect to the total mass of the butene-based resin composition. ),
Thermoplastic polyamide resin: For example, aliphatic polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612),
Thermoplastic polyester resin: for example, polyethylene terephthalate, polybutylene terephthalate, polyester elastomer,
Thermoplastic vinyl aromatic resin: For example, polystyrene, ABS resin, AS resin, styrene-based elastomer (styrene / butadiene / styrene block polymer, styrene / isoprene / styrene block polymer, styrene / isobutylene / styrene block polymer, hydrogenation of these object),
Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; vinyl acetate copolymer such as ethylene / vinyl acetate copolymer; ethylene / methacrylate acrylate copolymer; ionomer; ethylene / vinyl alcohol copolymer; polyvinyl Alcohol; Fluorine resin; Polycarbonate; Polyacetal; Polyphenylene oxide; Polyphenylene sulfide polyimide; Polyallylate; Polysulfone; Polyether sulfone; Rosin resin; Terpen resin and petroleum resin;
Copolymer rubber: For example, ethylene / α-olefin / diene copolymer, propylene / α-olefin / diene copolymer, 1-butene / α-olefin / diene copolymer, polybutadiene rubber, polyisobutylene rubber, neoprene. Rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, silicone rubber;
Etc. are exemplified.

Among the thermoplastic resins, low density, medium density, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 4-methyl-1-pentene, poly 3-methyl-1 are preferable. -Penten, poly3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer, 4-methyl-1-pentene / α -Olefin copolymers, styrene elastomers, vinyl acetate copolymers, ethylene / methacrylate acrylate copolymers, ionomers, fluororesins, rosin resins, terpene resins and petroleum resins, more preferably heat resistant. Polyethylene, isotactic polypropylene, syndiotactic polypropylene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin in terms of improvement, improvement of low temperature resistance, and flexibility. Polymers, 4-methyl-1-pentene / α-olefin copolymers, vinyl acetate copolymers, styrene-based elastomers, rosin-based resins, terpene-based resins and petroleum resins.

Part or all of the other polymer (C) may be graft-modified with a polar monomer. The details of graft denaturation will be described later in the column of << Graft denaturation >>.
The other polymer (C) may be used alone or in combination of two or more.

<< Additive (D) >>
Examples of the additive (D) include nucleating agents, antiblocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, and surfactants. , Antistatic agent, Weather-resistant stabilizer, Heat-resistant stabilizer, Anti-slip agent, Foaming agent, Crystallization aid, Anti-fog agent, Anti-aging agent, Hydrochloride absorber, Impact improver, Cross-linking agent, Co-cross-linking agent, Cross-linking aid Examples include agents, adhesives, softeners and processing aids.

The additive (D) may be used alone or in combination of two or more.
The content of the additive (D) is not particularly limited depending on the intended use as long as the object of the present invention is not impaired, but the additive to be blended with respect to the total mass of the butene-based resin composition of the present invention. It is preferably 0.001 to 30% by mass for each.

As the nucleating agent, a known nucleating agent can be used in order to further improve the moldability of the butene-based resin composition, that is, to raise the crystallization temperature and increase the crystallization rate. Specifically, divendilidene sorbitol-based nucleating agent, phosphate ester salt-based nucleating agent, rosin-based nucleating agent, benzoate metal salt-based nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di-t). -Butylphenyl) Sodium phosphate, pimelic acid and salts thereof, 2,6-naphthalene acid dicarboxylic acid dicyclohexylamide, ethylene bisstearate amide and the like can be mentioned.

The blending amount of the nucleating agent is not particularly limited, but is preferable with respect to 100 parts by mass of the total content of the butene / α-olefin copolymer (A), polybutene-1 (B) and other polymer (C). Is 0.001 to 5 parts by mass. The nucleating agent can be appropriately added during polymerization, after polymerization, or during molding.

As the anti-blocking agent, a known anti-blocking agent can be used. Specifically, fine powder silica, fine powder aluminum oxide, fine powder clay, powdery or liquid silicon resin, tetrafluoroethylene resin, fine powder crosslinked resin, for example, crosslinked acrylic, methacrylic resin powder, amido-based lubricant, etc. Can be mentioned. Of these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferable.

Examples of the pigment include an inorganic content (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and an organic pigment (azolake-based, thioindigo-based, phthalocyanine-based, anthraquinone-based). Examples of the dye include azo type, anthraquinone type, triphenylmethane type and the like. The amount of these pigments and dyes added is not particularly limited, but is usually 5% by mass or less, preferably 0.1 to 3% by mass, in total with respect to the total mass of the butene-based resin composition of the present invention.

Examples of the filler include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal. Examples thereof include oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate) and various metal (magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, and glass flakes.

Examples of the lubricant include wax (carnauba wax, etc.), higher fatty acid (stearic acid, etc.), higher alcohol (stearyl alcohol, etc.), and higher fatty acid amide (stearic acid amide, etc.).

Examples of the plasticizer include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methyl acetyl ricinolate, etc.), aliphatic dialbon acid esters (adipic acid-propylene glycol-based polyester, etc.), and aliphatic acids. Examples thereof include tricarboxylic acid esters (triethyl citrate and the like), phosphate triesters (triphenyl phosphate and the like), epoxy fatty acid esters (epoxybutyl stearate and the like), and petroleum resins.

Examples of the release agent include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hardened paraffin oil, etc.), glycol esters of fatty acids, and fluidized fatty acids. Examples include paraffin.

As the antioxidant, a known antioxidant can be used. Specifically, phenol-based (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenol-based (2,2'-methylenebis (4-methyl-6-t-butylphenol, etc.), phosphorus) System (tri (2,4-di-t-butylphenyl) phosphate, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate, etc.), sulfur system (thiodipropion) Examples thereof include dilauryl acid acid), amine-based (N, N-diisopropyl-p-phenylenediamine, etc.), and lactone-based antioxidants.

Examples of the flame retardant include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). ).

Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based ultraviolet absorbers.
Examples of the antibacterial agent include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodine.

Examples of the surfactant include nonionic, anionic, cationic or amphoteric surfactants. Examples of the nonionic surfactant include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, and polypropylene glycol ethylene oxide adduct, polyethylene oxide, and glycerin. Examples thereof include polyhydric alcohol type nonionic surfactants such as fatty acid esters, pentaerythritol fatty acid esters, sorbit or sorbitan fatty acid esters, polyhydric alcohol alkyl ethers, and alkanolamine aliphatic amides. Examples of the anionic surfactant include sulfate ester salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates, and higher alcohol phosphate ester salts. Examples include phosphoric acid ester salts. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric tenside include amino acid type double-sided surfactants such as higher alkylaminopropionate, higher alkyldimethylbetaine, and betaine type amphoteric surfactants such as hydroxyethyl betaine at higher alkyl.

Examples of the antistatic agent include the above-mentioned surfactant, fatty acid ester, and polymer type antistatic agent. Examples of the fatty acid ester include esters of stearic acid and oleic acid, and examples of the polymer antistatic agent include polyether ester amides.

Examples of the heat-resistant stabilizer include conventionally known stabilizers such as amine-based stabilizers, phenol-based stabilizers, and sulfur-based stabilizers. Specifically, aromatic secondary amine-based stabilizers such as phenylbutylamine and N, N'-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene and tetrakis [methylene (3,5-di-t-). Butyl-4-hydroxy) hydrocinnamate] Phenolic stabilizers such as methane, octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; bis [2-methyl-4- (3-) N-alkylthiopropionyloxy) -5-t-butylphenyl] thioether-based stabilizers such as sulfides; dithiocarbamate-based stabilizers such as nickel dibutyldithiocarbamate; zinc salts of 2-mercaptobenzoylimidazole and 2-mercaptobenzoimidazole; Examples thereof include sulfur-based stabilizers such as dilaurylthiodipropionate and distearylthiodipropionate. These stabilizers may be used alone or in combination of two or more.

As the cross-linking agent, for example, an organic peroxide is used.
Examples of the organic peroxide include dicumyl organic peroxide, di-tert-butyl organic peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-di. -(Tart-butylperoxy) hexin-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl- 4,4-Bis (tert-butylperoxy) peroxide, benzoyl organic peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl organic peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate , Diacetyl organic peroxide, lauroyl organic peroxide, tert-butylcumyl organic peroxide and the like.

The organic peroxide is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total content of the butene / α-olefin copolymer (A), polybutene-1 (B) and the other polymer (C). It is used in the ratio of.

Sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, and tri Peroxy cross-linking aids such as methylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimerol propanetrimethacrylate, Polyfunctional methacrylate monomers such as allyl methacrylate and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

By using the above compound, a uniform and mild cross-linking reaction can be expected. In particular, in the present invention, divinylbenzene is preferably used. Divinylbenzene is easy to handle, has good compatibility with polymers, has an action of solubilizing organic peroxides, and acts as a dispersant for organic peroxides. Therefore, a homogeneous cross-linking effect can be obtained, and a dynamic heat-treated product having a good balance between fluidity and physical properties can be obtained.

The cross-linking aid is preferably 0.05 to 10 with respect to 100 parts by mass of the total content of the butene / α-olefin copolymer (A), polybutene-1 (B) and other polymer (C). Used in proportion by mass.

Examples of the softening agent include process oils, lubricating oils, paraffins, liquid paraffins, petroleum asphalt, mineral oil-based softeners such as vaseline, coaltal-based softeners such as coaltal and coaltal pitch, castor oil and rapeseed oil. Fatty oil-based softeners such as soybean oil and palm oil, waxes such as tall oil, dense wax, carnauba wax and lanolin, fatty acids such as ricinolic acid, palmitic acid, stearic acid, barium stearate and calcium stearate or metal salts thereof. Naphthenic acid or its metal soap, pine oil, rosin or its derivatives, terpene resin, petroleum resin, kumaron inden resin, synthetic polymer substances such as atactic polypropylene, ester-based plastics such as dioctylphthalate, dioctyl adipate, dioctyl sebacate, etc. Agents, carbonate ester-based plasticizers such as diisododecyl carbonate, other microcrystallin wax, sub (factis), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, hydrocarbon-based synthetic lubricating oil and the like can be mentioned. Of these, petroleum-based softeners and hydrocarbon-based synthetic lubricating oils are preferable.

The amount of the softener is not particularly limited, but is 1 to 1 to 100 parts by mass based on 100 parts by mass of the total content of the butene / α-olefin copolymer (A), polybutene-1 (B) and other polymer (C). The amount is preferably 200 parts by mass. The softener facilitates processing when preparing the butene-based resin composition and assists in the dispersion of carbon black and the like.

《Graft denaturation》
Examples of the polar monomer used for graft modification include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid or a derivative thereof. , Vinyl ester compounds, vinyl chloride, carbodiimide compounds and the like. In particular, unsaturated carboxylic acids or derivatives thereof are preferred. Examples of the unsaturated carboxylic acid or a derivative thereof include an unsaturated compound having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, and an unsaturated compound having one or more anhydrous carboxylic acid groups. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group.

Specific examples of the polar monomer include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid [trademark] (endosis-bicyclo [2.2.1]. ] An unsaturated carboxylic acid such as hepto-5-ene-2,3-dicarboxylic acid) and a derivative of the unsaturated carboxylic acid include, for example, acid halides, amides, imides, anhydrides and esters. Specific examples of such derivatives include malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

These unsaturated carboxylic acids and / or their derivatives may be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferably used.

The modification is obtained by graft-polymerizing a polar monomer on the object to be modified. When the polar monomer is graft-polymerized on the modified product, the polar monomer is usually used in an amount of 1 to 100 parts by mass, preferably 5 to 80 parts by mass with respect to 100 parts by mass of the modified product. This graft polymerization is usually carried out in the presence of a radical initiator.

As the radical initiator, an organic peroxide, an azo compound and the like can be used. The radical initiator can be used as it is by mixing it with the denatured product and the polar monomer, or it can be used after being dissolved in a small amount of an organic solvent. The organic solvent can be used without particular limitation as long as it is an organic solvent capable of dissolving the radical initiator.

When the polar monomer is graft-polymerized on the modified product, a reducing substance may be used. When a reducing substance is used, the amount of grafted polar monomer can be improved.
The graft modification of the modified product with the polar monomer can be carried out by a conventionally known method. For example, the modified product is dissolved in an organic solvent, and then the polar monomer and the radical initiator are added to the solution, and the temperature is usually 70 to 200 ° C. It can be carried out by reacting at a temperature of 80 to 190 ° C., usually for 0.5 to 15 hours, preferably 1 to 10 hours.

It is also possible to produce a butene-based resin composition containing the modified product by reacting the modified product with the polar monomer using an extruder or the like. This reaction is usually carried out above the melting point of the object to be denatured. Specifically, when modifying the thermoplastic resin, it is desirable that the modification is carried out at a temperature of, for example, usually 120 to 300 ° C, preferably 120 ° C to 250 ° C, for usually 0.5 to 10 minutes. When the butene / α-olefin copolymer (A) is modified, it is desirable that the modification is carried out, for example, at a temperature of usually 160 to 300 ° C., preferably 180 ° C. to 250 ° C., for usually 0.5 to 10 minutes.

The amount of modification of the modified product thus obtained (the amount of graft of the polar monomer) is usually 0.1 to 50% by mass, preferably 0.2 to 30% by mass, when the modified product is 100% by mass. More preferably, it is 0.2 to 10% by mass.

In the present invention, the above-mentioned modified product and one or more of the unmodified products selected from the unmodified products of the butene / α-olefin copolymer (A) and the unmodified products of the other polymers (C). Can also be kneaded to obtain a butene-based resin composition.

Further, the butene-based resin composition of the present invention may be modified by containing a polar monomer. The content of the polar monomer is not particularly limited, but is preferably 0.001 to 50% by mass, more preferably 0.001 to 10% by mass, still more preferably 0.% by mass, based on 100% by mass of the butene-based resin composition. It is 001 to 5% by mass, most preferably 0.01 to 3% by mass. The content of the polar monomer can be easily designed according to the purpose, for example, by appropriately selecting the graft conditions.

It can also be graft-modified with a silane coupling agent. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltricrolsilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N. -(2-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glysidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3- (Triethoxysilyl) -1-propaneamine, N, N'-bis (3- (trimethoxysilyl) propyl) ethylenediamine, polyoxyethylenepropyltrialkoxysilane, polyethoxydimethylsiloxane, p-styryltrimethoxysilane, 3 -Acryloxypropyltrimethoxysilane can be mentioned.

When cross-linking with a silane coupling agent, either a dry treatment method or a wet (slurry method) treatment method may be used. Hydrocrosslinking of a polymer using a silane coupling agent can obtain a uniform crosslinked state, and is used in applications where strength and durability are required for industrial electric wires, pipes, and the like.

When the modified product is used, the adhesiveness and compatibility with other resins may be excellent, and the wettability of the surface of the obtained molded product may be improved. Further, by using the modified product, it may be possible to add compatibility or adhesiveness with other materials.

Further, when the amount of the graft of the polar monomer (eg, unsaturated carboxylic acid and / or its derivative) is in the above range, the graft of the butene / α-olefin copolymer (A) and / or the above-mentioned thermoplastic resin The composition containing the graft body of the above exhibits high adhesive strength to a polar group-containing resin (for example, polyester, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyamide, PMMA, polycarbonate, etc.).

[Manufacturing method of butene-based resin composition]
The method for producing the butene-based resin composition of the present invention is not particularly limited, and for example, the butene-α-olefin copolymer (A), the polybutene-1 (B), and an optional component, if necessary, are used. Examples thereof include a method of mixing at the above-mentioned addition ratio and then melt-kneading, or dissolving in a good solvent and sufficiently stirring, and then drying the solvent.

The method of melt-kneading is not particularly limited, and it can be carried out by using a melt-kneading device such as a generally commercially available extruder. For example, the temperature of the portion to be kneaded by the melt kneading device is usually 120 to 250 ° C, preferably 120 to 230 ° C. The kneading time is usually 0.5 to 30 minutes, particularly preferably 0.5 to 5 minutes.

Mixing in a solvent is possible as long as the solvent is not particularly limited and the butene / α-olefin copolymer (A) and polybutene-1 (B) can be dissolved. For example, it can be dissolved in hot xylene.

[Molded product]
Various molded bodies formed from the butene-based resin composition of the present invention can be widely used in conventionally known polyolefin applications. The molded body is obtained by a known heat molding method such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding and the like. Will be.

The thickness of the molded product is not particularly limited and can be appropriately determined depending on the intended use, but is usually in the range of 0.1 to 20 mm, preferably 0.15 to 10 mm (excluding the stretched film). Within this range, the balance between rigidity and uniform workability is good.

The shape of the extruded body and the type of product are not particularly limited. Examples include sheets, stretched or unstretched films, pipes, hoses, wire coatings, tubes, and in particular sheets (skin materials), films, tubes, catheters, monofilaments, multifilaments, non-woven fabrics.

Conventionally known extruders and molding conditions can be adopted for extrusion molding. For example, the butene-based resin melted by using a single-screw screw extruder, a kneading extruder, a ram extruder, a gear extruder, or the like can be used. The composition can be formed into a desired shape by extruding the composition from a specific die or the like.

The stretched film can be obtained by stretching an extruded sheet or an extruded unstretched film as described above by a known stretching method such as a tenter method (longitudinal horizontal stretching, horizontal vertical stretching), a simultaneous biaxial stretching method, or a uniaxial stretching method. Can be done. The draw ratio when stretching a sheet or an unstretched film is usually about 20 to 70 times in the case of biaxial stretching, and usually about 2 to 10 times in the case of uniaxial stretching. By stretching, a stretched film having a thickness of 1 to 500 μm, preferably about 5 to 200 μm can be obtained.

The filament molded product can be produced, for example, by extruding the melted butene-based resin composition through a spinneret. The filament thus obtained may be further stretched. This stretching may be performed so that at least one axial direction of the filament is molecularly oriented, and it is usually desirable to perform this stretching at a magnification of about 5 to 10 times. The filament is excellent in transparency, rigidity, heat resistance, impact resistance and elasticity. Specifically, the nonwoven fabric can be produced by using a spunbond method or a meltblown method.

As the injection-molded article, the butene-based resin composition can be produced by injection-molding into various shapes by using a conventionally known injection-molding apparatus and adopting known conditions. Injection molded products are not easily charged and have excellent transparency, rigidity, heat resistance, impact resistance, surface gloss, chemical resistance and abrasion resistance, and are excellent in pipe fittings, trim materials for automobile interiors, and exteriors for automobiles. It can be widely used for materials, housings for home appliances, containers, etc.

Inflation film can also be manufactured as a film. Inflation films include, for example, daily miscellaneous goods packaging materials, food packaging materials, food containers, retort containers, protective films, decorative films / sheets, shrink films, infusion bags, heat fusion films, stretched films, raw material films for stretching, medical treatment. It can be suitably used as a material for containers and the like.

Here, the shrink film can be obtained by stretching a film made of the butene-based resin composition of the present invention uniaxially or biaxially in a temperature range of usually 60 to 100 ° C., preferably 60 to 80 ° C. Examples of the stretching method include stretching methods of polyolefin resin films (eg, uniaxial stretching and biaxial stretching) which are conventionally performed, and examples thereof include uniaxial stretching methods using a heating roll, and biaxial stretching methods include biaxial stretching methods. , Simultaneous biaxial stretching method by tubular method, sequential biaxial stretching method by heating roll / tenter, or simultaneous biaxial stretching method by tenter. The stretch ratio of the film is usually 3 times or more, preferably 3 to 10 times, and more preferably 4 to 8 times.

In addition, sheets and films are not easily charged and have excellent rigidity such as tensile elastic modulus, heat resistance, elasticity, impact resistance, aging resistance, transparency, transparency, gloss and heat sealability, and are suitable for packaging. It can be widely used as a film, a protective film, and the like. In this case, the sheet and the film may be a laminated body (laminated sheet, film).

Here, the laminated film is a method of extruding and laminating the butene-based resin composition of the present invention on at least one surface of the base film, and an anchor coating agent for the base film and the film composed of the butene-based resin composition of the present invention. By various known production methods, such as a method of making a dry laminate by using it, or a method of obtaining a coextruded film of a thermoplastic polymer used as a raw material of a base film and a butene-based resin composition of the present invention using a multilayer die. Can be manufactured. In the laminated film of the present invention, the thickness of the film made of the butene-based resin composition is usually 5 to 500 μm, preferably 10 to 300 μm, and more preferably 20 to 200 μm.

The blow-molded product can be produced by blow-molding a butene-based resin composition using a conventionally known blow-molding apparatus and adopting known conditions. In this case, the blow molded body may be a multi-layer molded body.

For example, in extrusion blow molding, the butene-based resin composition is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison is held in a mold having a desired shape and then air. Can be manufactured by blowing in a hollow molded article and mounting it on a mold at a resin temperature of 130 ° C. to 300 ° C. The stretch (blow) magnification is preferably about 1.5 to 5 times in the lateral direction.

For example, in injection blow molding, the butene-based resin composition is injected into a parison mold at a resin temperature of 100 ° C. to 300 ° C. to form a parison, and then the parison is held in a mold having a desired shape and then air is blown into the parison. A hollow molded product can be manufactured by mounting on a mold at a resin temperature of 120 ° C. to 300 ° C. The stretch (blow) magnification is preferably 1.1 to 1.8 times in the vertical direction and 1.3 to 2.5 times in the horizontal direction.

The blow molded article is excellent in transparency, rigidity or flexibility, heat resistance and impact resistance, and also excellent in moisture resistance. Blow molded articles include, for example, foods, seasonings, cosmetics, hairdressing agents, drinking water, refreshing drinking water, carbonated beverages, alcohols, bleaching agents, detergents, shampoos, rinses, conditioners, softeners, softening agents, chemicals, etc. It can be used for adhesives, pesticides, medical products, baby bottles, laboratory equipment, kerosene cans, containers such as generators, lawnmowers, motorcycles, automobiles and other gasoline tanks, bottles and cups.

In press molding, for example, the melt-kneaded product of the butene-based resin composition is pressed at 5 to 20 MPa for 1 to 15 minutes using a press machine set at 120 to 250 ° C. If necessary, use a press machine set at 10 to 20 ° C. and pressurize and cool at 5 to 20 MPa for 1 to 15 minutes. In this way, the press sheet can be obtained. The thickness of the press sheet is, for example, 0.1 to 6.0 mm.

Examples of the press-molded body include a mold stamping molded body. For example, the butene-based resin composition is used as a base material when a base material and a skin material are press-molded at the same time and both are compositely integrated and molded (mold stamping molding). Things can be used. Specific examples of such a mold stamping molded body include automobile interior materials such as door trims, rear package trims, seat back garnishes, and instrument panels. The press-molded article is not easily charged and is excellent in rigidity or flexibility, heat resistance, transparency, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance and the like.

In the case of manufacturing using a molded body by vacuum forming, for example, the butene-based resin composition is vacuum-formed after obtaining a sheet or a film by a known extrusion process. The thickness of the sheet or film is not particularly limited, but is preferably 0.1 to 3 mm, for example.

There are no particular restrictions on the vacuum forming method. Usually, the sheet or film-shaped molded product is heated and softened to be brought into close contact with the mold, air is discharged from the exhaust port provided in the mold, the molded product is brought into close contact with the mold, and then the molded product is cooled. The next processed molded product can be manufactured.

The surface temperature of the molded product during vacuum forming is usually in the temperature range of 120 to 250 ° C., preferably in the temperature range of 120 to 220 ° C., and more preferably in the temperature range of 120 to 200 ° C. When the surface temperature is within the above range, the draw-down property and the shapeability are good, and the wall thickness becomes uniform.

The vacuum formed body is, for example, an automobile interior material, an automobile exterior material, a packaging case, a protective case, a protective sheet, a container for food / beverage, a bottle, a cup, a case for an information terminal, a protective cover for an information terminal, and the like. It can be suitably used for a frame / cover for a display material, furniture, and a frame for furniture.

In the present invention, it is also possible to manufacture a vacuum formed body such as an instrument panel of an automobile and an interior skin material such as a door trim. The molded product is not easily charged and is excellent in flexibility, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance and the like.

In the present invention, powder slash molded products such as automobile parts, home electric appliance parts, toys, and miscellaneous goods can also be manufactured. The molded product is not easily charged and is excellent in flexibility, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance and the like.

As the molded product of the present invention, a multilayer molded product having at least one layer made of the butene-based resin composition of the present invention can also be mentioned. The multilayer molded product is a molded product in which at least one layer thereof is a layer formed from the butene-based resin composition of the present invention. Specific examples thereof include a multilayer film, a multilayer sheet, a multilayer container, a multilayer tube, a multilayer pipe, and a multilayer coating film laminate contained as one component of a water-based paint.

The butene-based resin composition of the present invention is suitable as a material for forming a container or a non-woven fabric, for example. Examples of the container include a freezing storage container, a food container such as a retort pouch, and a bottle container. In addition, medical containers, infusion bags, etc. can be exemplified.

Since the butene-based resin composition of the present invention has the above-mentioned characteristics, it can be used as a tank such as a pipe, a pipe joint, a blow tank, a sheet, an unstretched or stretched film, a filament, or a molded body having various other shapes. be able to. Examples of the blow tank include a water supply / hot water supply tank. Among these, pipes and pipe joints are preferable, and they are used for gas transportation, etc., and more preferably, for water / hot water supply, underfloor heating, hot water heating, hot spring piping, chemical spraying, drainage, watering, etc. Used for liquid transport pipes and fittings for washing machines, dishwashers, toilets, bathrooms, solar systems, mist generators, farming, etc., and particularly preferably water / hot water supply pipes and fittings. ..

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
[Synthesis of transition metal complex]
According to Synthesis Example 4 of WO2014 / 050817, (8-octamethylfluorene-12'-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6, 7,7a, 8-octahydrocyclopenta [a] indene)) Zirconium dichloride was synthesized. This compound is also referred to as "catalyst (a)".

[Comparative Example 1] A conventionally known butene using the Ti-based catalyst described in [Production Example 1] of JP-A-2002-241553, except that the total pressure of the 1-butene / propylene copolymer is 0.5 MPaG. An evaluation polymer (1-butene / propylene binary copolymer) was synthesized by the polymerization method of the system polymer.

[Comparative Example 2] The same operation as in Comparative Example 1 was performed except that the total pressure of the 1-butene / propylene copolymer was changed to 0.6 MPaG, and the evaluation polymer (1-butene / propylene binary copolymer) was performed. Was synthesized.

[Production Example 1] 1-Butene homopolymer A magnetic stirrer is placed in a Schlenk tube that has been sufficiently dried and substituted with nitrogen, a catalyst (a) 2.0 μmol is added as a metallocene compound, and a suspension of modified methylaluminoxane is used as a catalyst ( Add 300 equivalents (n-hexane solvent, 0.60 mmol in terms of aluminum atom) to a) at room temperature with stirring, and then add heptane in an amount that makes the catalyst (a) 1 μmol / mL, and add the catalyst solution. (A) was prepared.

A SUS autoclave having an internal volume of 1,500 ml that had been sufficiently dried and replaced with nitrogen was charged with 500 mL of heptane and 1.5 mL of a hexane solution of triisobutylaluminum (Al = 0.5M, 0.75 mmol) as a polymerization solvent. Then, 180 g of 1-butene was added with stirring at 850 rpm, and then the polymerization temperature was raised to 60 ° C. After adding 284 NmL of hydrogen at that temperature, nitrogen was added until the autoclave internal pressure reached 0.5 MPaG.

The catalyst solution prepared above was charged into the autoclave to start the polymerization, the total pressure was maintained at 0.5 MPaG until the polymerization was stopped, and methanol was added 20 minutes after the start of the polymerization to stop the polymerization.
The polymer solution taken out from the cooled / depressurized autoclave was put into methanol to precipitate the polymer, and the polymer was collected by filtration. Then, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain an evaluation polymer (1-butene homopolymer).

[Production Example 2] 1-Butene homopolymer In a SUS autoclave having an internal volume of 1,500 ml that has been sufficiently dried and substituted with nitrogen, 500 mL of heptane and a hexane solution of triisobutylaluminum as a polymerization solvent (Al = 0.5M, 0. (75 mmol) 1.5 mL was charged, and then 180 g of 1-butene was added while stirring at 850 rpm, and then the polymerization temperature was raised to 60 ° C. After adding 71.0 NmL of hydrogen at that temperature, nitrogen was added until the autoclave internal pressure reached 0.7 MPaG.

The catalyst solution (a) prepared in Production Example 1 was charged into this autoclave to start polymerization, and methanol was added 15 minutes after the start of polymerization to terminate the polymerization.
The polymer solution taken out from the cooled / depressurized autoclave was put into methanol to precipitate the polymer, and the polymer was collected by filtration. Then, the recovered polymer was dried under reduced pressure at 80 ° C. for 10 hours to obtain a polymer for evaluation (1-butene homopolymer).

[Production Example 3] 1-Butene homopolymer The same operation as in Comparative Example 1 was carried out except that propylene was not used, and a polymer for evaluation (1-butene homopolymer) was synthesized.

[Comparative Example 3] Butene Polymer Blend The 1-butene / propylene copolymer obtained in Comparative Example 1 and the 1-butene homopolymer obtained in Production Example 3 have a mass ratio of 75:25. Weighed into a sample bottle containing a magnetic stirrer. A p-xylene solution was added, and the mixture was placed in a hot stirrer set at 140 ° C. to dissolve and stirred. After 1 hour, it was confirmed that there were no undissolved substances, and the solution was developed on a glass petri dish and left overnight at room temperature. The next day, the solid after the solvent had evaporated was further dried at 120 ° C. in a nitrogen atmosphere for 24 hours to obtain a resin composition.

[Example 1] Butene-based polymer blend The resin as a raw material and its ratio are 95% by mass of the 1-butene / propylene copolymer obtained in Comparative Example 1 and 1-butene alone obtained in Production Example 1. The same operation as in Comparative Example 3 was carried out except that the polymer was changed to 5% by mass to obtain a resin composition.

[Example 2] Butene-based polymer blend The raw material resin and its ratio were 75% by mass of the 1-butene / propylene copolymer obtained in Comparative Example 1 and 1-butene alone obtained in Production Example 1. The same operation as in Comparative Example 3 was carried out except that the polymer was changed to 25% by mass to obtain a resin composition.

[Example 3] Butene-based polymer blend The resin as a raw material and its ratio were 75% by mass of the 1-butene / propylene copolymer obtained in Comparative Example 1 and 1-butene alone obtained in Production Example 2. The same operation as in Comparative Example 3 was carried out except that the polymer was changed to 25% by mass to obtain a resin composition.

[Example 4] Butene-based polymer blend The resin as a raw material and its ratio were 75% by mass of the 1-butene / propylene copolymer obtained in Comparative Example 2 and 1-butene alone obtained in Production Example 1. The same operation as in Comparative Example 3 was carried out except that the polymer was changed to 25% by mass to obtain a resin composition.

[Measurement conditions for various physical properties]
Various physical properties of the polymer or resin composition obtained in Examples and the like were measured by the following methods. The results are shown in Table 1.

[Comonomer composition]
The content of the propylene-derived structural unit (comonomer unit) in the butene / α-olefin copolymer was calculated from the ¹³ C-NMR spectrum by the following equipment and conditions.

Using AVANCE III cryo-500 type nuclear magnetic resonance device manufactured by Bruker Biospin, the solvent is o-dichlorobenzene / benzene-d ₆ (4/1 v / v) mixed solvent, the sample concentration is 60 mg / 0.6 mL, and the measurement temperature is measured. 120 ° C, observation nucleus ¹³ C (125 MHz), sequence single pulse proton broadband decoupling, pulse width 5.0 μsec (45 ° pulse), repetition time 5.5 seconds, integration count 128 times, benzene The side chain methylene signal of 27.5 ppm was measured as a reference value for chemical shift. Using the integrated value of the main chain methylene signal, the content of comonomer units was calculated by the following formula.
Content of comonomer unit (mol%) = [P / (P + M)] × 100
Here, P indicates the total peak area of the comonomer backbone methylene signal, and M indicates the total peak area of the 1-butene backbone methylene signal.

[Mmm fraction]
The mmmm fraction (%) is expressed by the following formula.
mmmm fraction (%) = Smmmm / S × 100
Here, in the ¹³ C-NMR spectrum, Smmmm shows the peak area of the butene side chain methylene signal derived from mm mm having a peak top of 27.50 ppm, and S appears in the range of 29.0 ppm to 25.0 ppm on the butene side. The total peak area of the chain methylene signal is shown.

[Rr fraction]
The rr fraction (%) is expressed by the following formula.
rr fraction (%) = Srr / S × 100
Here, in the ¹³ C-NMR spectrum, Srr indicates the peak area of the butene side chain methylene signal derived from rr appearing in the range of 26.6 ppm to 25.0 ppm, and S appears in the range of 29.0 ppm to 25.0 ppm. , The total peak area of the butene side chain methylene signal.

[Ultimate viscosity [η]]
The ultimate viscosity [η] of the butene-based polymer was measured at 135 ° C. using decalin. Specifically, about 20 mg of the butene-based polymer obtained by the above polymerization was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin to this decalin solution and diluting it, the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated twice more, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity (see the formula below).
[Η] = lim (ηsp / C) (C → 0)

[Ratio of molecular weight of 10,000 or less]
The proportion of the components of the butene polymer having a molecular weight of 10,000 or less was determined by gel permeation chromatography (GPC) as columns of TSKgelGMH6-HT x 2 and TSKgelGMH6-HTL x 2 manufactured by Tosoh Corporation (column size is any). The measurement was performed using a liquid chromatograph (Alliance / GPC2000 type manufactured by Waters) in which (7.5 mm in diameter and 300 mm in length) were connected in series. The mobile phase medium uses o-dichlorobenzene and 0.025% by mass of BHT (Takeda Pharmaceutical) as an antioxidant, the sample concentration is 0.15% (V / W), the flow rate is 1.0 ml / min, and the temperature is 140 ° C. Measurements were made. As the standard polystyrene, Tosoh Corporation was used for the molecular weight of 500 to 20,600,000. The obtained chromatogram was analyzed by a known method using Waters data processing software Emper2 using a calibration curve using a standard polystyrene sample, and the ratio of components having a molecular weight of 10,000 or less was calculated.

[Cool of heat ΔH]
The heat generation / endothermic curve was obtained by a DSC measuring device (Diamond DSC) manufactured by Parkin Elma, and the heat of fusion ΔH was calculated from the integrated value of the maximum melting peak at the time of temperature rise.

The measurement was performed as follows. Approximately 5 mg of the sample was cut out, filled in an aluminum pan for measurement, heated from 30 ° C to 200 ° C at a heating rate of 500 ° C / min, held at 200 ° C for 5 minutes, and then 30 ° C at a cooling rate of 10 ° C / min. After lowering the temperature to 30 ° C. and holding at 30 ° C. for 5 minutes, the temperature was raised again from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min. ΔH was calculated from the integrated value of the melting peaks that appeared during the second temperature rise.

[Half crystallization time τ _1/2 ]
The semi-crystallization time τ _1/2 was measured using a DSC measuring device (Diamond DSC) manufactured by Parkin Elma. The temperature is raised from 30 ° C. to 320 ° C./min at a set rate of 200 ° C., held for 10 minutes, and then lowered to 85 or 80 ° C. at a set rate of 320 ° C./min to obtain a crystallization peak under isothermal temperature. It was measured. From the measured crystallization peak, the time from the time when crystallization started to the time when crystallization is half accelerated (when the area becomes 1/2 of the total crystallization peak area) is τ _1/2 . And said.

Comparison between Examples and Comparative Examples FIG. 1 is a plot of the heat of fusion ΔH with respect to the proportion (mass percent) of polybutene-1 in the examples and the like. The dotted line in the figure connects the single butene-propylene copolymer and the heat of fusion ΔH value of polybutene-1 forming the blend. The fact that each blend shows a heat of fusion ΔH larger than the dotted line indicates that simple additivity does not hold. Therefore, it can be said that the addition of polybutene-1 has a crystallization promoting effect, and in particular, the effect of adding polybutene-1 having a large mmmm fraction and a small rr fraction as shown in the examples is remarkable. be.

FIG. 2 is a plot of the semi-crystallization time at a crystallization temperature of 85 ° C. with respect to the proportion (mass percent) of polybutene-1 in Examples and the like. It can be said that polybutene-1 (Production Examples 1 and 2) having a large mm mm fraction and a small rr fraction has a shorter semi-crystallization time and a faster crystallization rate than Production Example 3. The crystallization rate of the butene-propylene copolymer is slower than that of polybutene-1. By blending polybutene-1, which has a faster crystallization rate than the main component, butene-propylene copolymer, the semi-crystallization time of the blend was shortened. By mixing polybutene-1 having a high crystallization rate in this way, they became nuclei and could promote the crystallization of the blend.

Claims (3)

70 to 99.9 parts by mass of a butene / α-olefin copolymer ( A) satisfying the following requirements (A1) to (A4), and polybutene-1 (B) satisfying the following requirements (B1) to (B4). A butene-based resin composition containing 0.1 to 30 parts by mass (however, the total of the butene / α-olefin copolymer (A) and polybutene-1 (B) is 100 parts by mass).
(A1): At least one selected from ethylene and α-olefins other than 1-butene having 3 to 20 carbon atoms and having a content of 1-butene-derived structural units of 80.0 to 99.9 mol%. The total content (K) of the constituent units derived from olefin is 0.1 to 20.0 mol%. (However, the total of the content of the constituent unit derived from 1-butene and the total content (K) is 100 mol%.)
(A2): The ultimate viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.5 dl / g.
(A3): The isotactic pentad fraction measured by ¹³ C-NMR is 90.0% or more and 92.3% or less.
(A4): The syndiotactic triad fraction measured by ¹³ C-NMR is 2.1% or more and 3.0% or less.
(B1): ¹³ The isotactic pentad fraction measured by C-NMR is 94.0% or more.
(B2): ¹³ The syndiotactic triad fraction measured by C-NMR is 1.5% or less.
(B3): The ultimate viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.5 dl / g.
(B4): The proportion of components having a molecular weight of 10,000 or less as measured by gel permeation chromatography (GPC) is less than 1.3% by mass. A molded product made of the butene-based resin composition according to claim 1. The molded product according to claim 2, which is a pipe or a pipe joint.

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