JPH03231963A - Thermoplastic polymer composition - Google Patents

Abstract

PURPOSE:To provide the subject composition having excellent heat resistance, mechanical strength, abrasion, etc., and suitable as a modifying material for various plastics, etc., by compounding a thermoplastic polyurethane, an olefinic polymer having specific functional group and, if necessary, an olefinic polymer having no functional group in specific amounts, respectively. CONSTITUTION:The objective composition comprises (A) 2-98wt.% of a thermoplastic polyurethane having a molecular weight of 5000-500000 and (B) 2-28wt.% of an olefinic resin having at least one kind of functional groups selected from carboxyl groups, acid anhydride groups and epoxy groups. On the objective composition comprises (A) 2-98wt.% of the thermoplastic poly urethane, (B) 1-35wt.% of the olefinic resin and (C) 1-97wt.% of an olefinic prelymer (e.g. ethylene-propylene copolymer) having no functional group.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a highly compatible thermoplastic polymer composition with excellent heat resistance, mechanical strength, and abrasion resistance, and more specifically, , thermoplastic polyurethane (hereinafter referred to as
ITPUJ), a carboxyl group, an acid anhydride group, an epoxy group, and optionally an olefin polymer without a functional group. .

[Conventional technology] TPU has excellent flexibility, tensile strength, tear strength, low-temperature properties, abrasion resistance, oil resistance, and bending fatigue resistance, and is often used in sports shoe soles, ski boots, various hoses, tubes, films, etc. It's being used.

However, it has disadvantages such as poor moldability such as water resistance and narrow optimum processing temperature range, and high density and high water absorption. Furthermore, this type of thermoplastic polymer is composed of soft segments of polyethers and polyesters, aromatic diisocyanates, ethylene glycol, and 1,4
- It is a multi-block copolymer composed of hard segments of polyurethane made of short chain diol of butanediol, and in order to exhibit the excellent properties of TPU, the amount of hard segments must be increased to a certain level. It is necessary to do so. Therefore, high-performance TPU materials must have high hardness and high elastic modulus, and at present, TPU with low hardness and low elastic modulus that maintains high performance has not been obtained.

[Problems to be Solved by the Invention] On the other hand, olefin polymers have excellent tensile strength and hot water resistance. Therefore, attempts have been made to combine TPU and olefin polymers.

However, TPU and olefin polymers have poor compatibility, and a composition comprising TPU and olefin polymers that has the expected performance has not yet been found.

[Means for Solving the Problems] The present invention provides (1) TPU (A) 2 to 98% by weight, and an olefin having at least one functional group selected from a carboxyl group, an acid anhydride group, and an epoxy group. A thermoplastic polymer composition consisting of 28 to 2% by weight of the polymer (B),
and (2) 2 to 98% by weight of thermoplastic polyurethane (A), 1 to 35% by weight of olefin polymer (B) having at least one functional group selected from carboxyl group, acid anhydride group, and epoxy group. , and an olefinic polymer (C) having no functional group in an amount of 1 to 97% by weight.

Component (A) The TPU used in the present invention is an elastomer obtained through a polyaddition reaction using long-chain polyols, short-chain glycols, diisocyanates, etc. as raw materials through urethane bonds in the molecule, and is used for shoe soles. , used in hoses, tubes, adhesives, etc. The long-chain polyol that is the raw material for this thermoplastic polyurethane contains poly(1,4-
butylene adipate), poly(1,6-hexane adipate), polycaprolactone, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and the like. In addition, short chain glycols include ethylene glycol, 1゜4-butanediol, 1
, 6-hexanediol, etc. Further diisocyanates include tolylene diisonanate, 4.4'
-Diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. and long-chain polyols and diisocyaners).
A soft segment is formed with short chain glycol and diisocyanate, and a hard segment is formed with short chain glycol and diisocyanate.

The molecular weight of the thermoplastic polyurethane is preferably 5.00.
0 to 500,000, more preferably 10,000 to
300,000.

(B) Component The olefin polymer having at least one functional group selected from a carboxyl group, an acid anhydride group, and an epoxy group used in the present invention is a raw material olefin and a functional group of the following olefin polymer. It is a polymer into which a functional group has been introduced by copolymerization with a monomer having the following, or a polymer reaction between the following olefin polymer and a monomer having a functional group.

The olefinic polymer contains at least 50 mol%, preferably more than 70 mol% of 1-olefins, such as ethylene, propylene, 1-butene, isobutane, 1-pentene, 1-hexene, 1-decene, 4-methyl- 1-butene, 4-methyl-1-pentene, 4,4-dimethyl-1-
Polymers of pentene or mixtures of the olefins listed above may be mentioned.

Preferable examples include copolymers of ethylene and propylene, ethylene and 1-butene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene, and the like.

Examples of the acid component used in the olefin polymer containing a carboxyl group or an acid anhydride group include acrylic acid, methacrylic acid, methacrylic acid, itaconic acid, maleic acid (anhydride), and fumaric acid (anhydride) cis-4- Cyclohexene-1
, 2-dicarboxylic acid, and monoester of -1-carboxylic acid, and preferred examples include acrylic acid, methacrylic acid, and maleic acid (anhydride).

Among these, maleic acid (anhydride) is particularly preferred since a sufficient acid modification effect can be obtained with addition of a small amount compared to other acids. Suitable carboxyl group-containing olefin polymers include:
Examples include maleic anhydride-modified ethylene-1-butene copolymer, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified polyethylene, and maleic anhydride-modified polypropylene.

Examples of the epoxy compound used in the epoxy group-containing olefin polymer include glycidyl esters of α,β-unsaturated carboxylic acids, which have the general formula % (wherein R is a hydrogen atom or a lower alkyl group). ) can be used, such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc., among which glycidyl methacrylate is preferred. Preferably used.

Such olefin polymers containing carboxyl groups, acid anhydride groups, and/or epoxy groups usually contain monomers having these functional groups in a concentration of 0.01 to 2.
The content is 0% by weight, preferably in the range of 0.05 to 15% by weight.

In the present invention, component (B) is an essential component to be composited with TPU, and can be used alone or when composited with an olefinic polymer having no functional group, which is component (C) described later. Acts as a compatibilizer.

Component (C) Component (C) is an olefin polymer that does not have a functional group such as a carboxyl group, an acid anhydride group, or an epoxy group,
Specifically, the same olefin polymers as exemplified in component (B) can be mentioned.

Preferred are ethylene-propylene copolymer, high density polyethylene, low density polyethylene, polypropylene and the like.

When component (C) is not used, the composition of each component of the present invention is TPU (A) 2 to 98% by weight, preferably 3 to 9% by weight.
5% by weight, more preferably 5 to 85% by weight, particularly preferably 10 to 80% by weight, an olefin polymer (B )2 to 28% by weight, preferably 3 to 28% by weight, more preferably 5 to 25% by weight
It is.

If the TPU content is less than 2% by weight, heat resistance and mechanical strength will be poor, and if the TPU content exceeds 98% by weight, a composition with low hardness and low elastic modulus cannot be obtained.

On the other hand, if the content of the olefinic polymer having a functional group is less than 2% by weight, the compatibility between TPU and the olefinic polymer not having a functional group will be insufficient, making it impossible to obtain a uniform composition. In addition, the olefin polymer having a functional group is 28
If it exceeds % by weight, the fluidity of the composition will be poor.

When using component (C), the composition of each component is TPU
(A) 2-98% by weight, preferably 3-95% by weight, more preferably 5-85% by weight, particularly preferably 10-95% by weight
80% by weight, olefin polymer (B) having at least one functional group selected from carboxyl group, acid anhydride group, and epoxy group 1 to 35% by weight, preferably 2 to 28% by weight, more preferably 3% by weight ~25% by weight, and 1 to 97% by weight of an olefinic polymer (C) having no functional group,
Preferably 3 to 90% by weight, more preferably 5 to 80% by weight
Weight%.

1% by weight of olefin polymer (C) without functional groups
If it is less than 97% by weight, the hot water resistance will be poor, and if it exceeds 97% by weight, the impact resistance, abrasion resistance, and oil resistance will be poor.

An olefinic polymer having no functional group can be blended as necessary because it effectively acts to lower the hardness and elastic modulus of the composition of the present invention.

In addition, if necessary, thermoplastic polymers such as polystyrene resins, diene resins, polyvinyl chloride resins, polyvinyl acetate resins, polycarbonate resins, polyacetal resins,
Polyamide resins, polyester resins, polyether resins, polysulfones, thermoplastic resins such as polyphenylene sulfide, styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated products thereof Styrene-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic glass) hemer, thermoplastic elastomer such as vinyl chloride-based thermoplastic elastomer, styrene-butadiengo 14, butadiene rubber, Elastomers of nitrile rubber, acrylic rubber, and hydrogenated nitrile rubber can be used in combination.

The composition of the present invention may also contain crosslinks such as sulfur crosslinks, peroxide crosslinks, resin crosslinks, metal ion crosslinks, electric r-ray crosslinks, and silane crosslinks, and these crosslinks are
This can be done in a static or dynamic manner.

Various known methods can be applied to prepare the composition of the present invention. For example, any conventionally known method may be used, such as an extruder (single-screw or twin-screw), mill, Panbury mixer, kneader, or Henschel mixer.

In addition, the thermoplastic polymer composition obtained by the above method can be molded into a practically useful molded product by conventionally known methods such as extrusion molding, injection molding, blow molding, compression molding, and calendering. Can be processed. Furthermore, processing such as painting and plating can be applied as necessary.

Furthermore, additives used for ordinary thermoplastic polymers can be added to the thermoplastic polymer composition of the present invention, if necessary. For example, plasticizers such as phthalate ester compounds, fillers or reinforcing agents such as silica, talc, and glass fibers, other antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, lubricants, foaming agents, colorants, Pigments, pigments,
Crosslinking agents, crosslinking aids, etc., or mixtures thereof can be added.

The thermoplastic polymer composition of the present invention has excellent heat resistance, abrasion resistance, processability, flexibility, low-temperature properties, 2. temperature dependence, compatibility, paintability, printability, hot stampability, and adhesiveness. By taking advantage of deep drawability, hot water resistance, rubber elasticity, rubber feel, flexibility, slip resistance, stress crack resistance, etc., we are developing various plastic improvement materials, footwear sole materials, adhesives and viscosity agents, It can be used for asphalt modification, vulcanized rubber modification, etc. For example, sheet applications such as meat and fresh fish trays, fruit and vegetable bags, frozen dessert food containers, food packaging, daily necessities packaging, industrial material packaging, film applications such as elastic tapes for disposable diapers, sports shoes, leisure shoes, and fashion sandals. , footwear such as leather shoes, home appliances such as televisions, stereos, vacuum cleaners, etc.
Automotive interior and exterior parts applications such as bumper parts, body panels, and sight shields; cumulative applications such as hot-melt adhesives and adhesives, contact adhesives, and spray adhesives; road paving materials, waterproof sheets, and piping. It can be used in a wide range of applications, including asphalt blend materials such as coatings, other daily necessities, leisure goods, toys, hoses, tubes, and industrial goods.

[Examples] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the examples unless it goes beyond the gist of the present invention.

(Reference Example 1) Maleic anhydride-modified ethylene-propylene comb (EP
Manufacturing method of M) Ethylene-propylene copolymer rubber (manufactured by Romoto Synthetic Rubber ■,
EP96], 5P) 100 parts, i, 3-bis (t e
0.5 parts of r t-butylperoxypropyl)benzene, and 0.5 parts of maleic anhydride. 5 parts were mixed and kneaded in an extruder set at a cylinder temperature of 220°C to form maleic anhydride-modified EPM pellets. Quantitative analysis using an infrared absorption spectrum confirmed that 0.30% by weight of maleic anhydride was added. This is called anhydrous 71twin acid-modified EPM4).

(Reference Example 2) The amount of maleic anhydride used in Reference Example 1 was changed to 1.0 parts by weight, and a maleic anhydride EPM-(2) with an added amount of maleic anhydride of 0.8% by weight was prepared.

(Reference Example 3) The amount of maleic anhydride used in Reference Example 1 was 1. A maleic anhydride-modified EPM-(3) was prepared in which the amount of maleic anhydride added was 1.2% by weight instead of 5 parts by weight.

Physical property evaluation method O Tensile properties Based on JIS K6301, 50% tensile stress (M)
, 100% tensile stress (Mloo), 300% tensile stress (M ), tensile strength (T8), and 00 elongation at break (EB) were determined.

0 Hardness I Measured using a JIS A hardness meter in accordance with JIS K6301.

O density The value at 23°C was determined by the buoyancy method.

0VICAT Softening Temperature Measured in accordance with ASTM D1044 under a load of 1 kg.

O Taper Wear 5 Measured using a worn wheel H-22 in accordance with ASTM D1044.

O Moisture Absorption Rate After vacuum drying at 80°C for 24 hours and leaving the test piece in an absolutely dry state for 24 hours at 20°C and 65% RH, the absorbed moisture was measured using a Karl Fischer moisture meter to determine the moisture absorption rate. Ta.

(Examples 1 to 3) Thermoplastic polyurethane (■ Kuramiron 319 manufactured by Kuraray)
0) To 75 parts by weight, 25 parts by weight of each of the maleic anhydride-modified EPM-(11 to (3)) prepared in Reference Examples 1 to 3 was kneaded using a plastomill at 190°C, 60 rpm, for 5 minutes to obtain a blend. The kneaded product was press-molded, compression-molded test pieces were prepared, and various physical properties were measured.The results are shown in Table 1.

(Examples 4 to 12) Ethylene-propylene copolymer rubber (Japanese Synthetic Rubber ■
EP33) and (maleic anhydride-modified EPM-(2)
) were kneaded at the composition ratio shown in Table 1 and similarly evaluated as 6. The results are shown in Table-1.

(Examples 13 to 14) Instead of the maleic anhydride acidic EPM (2) used in Example 5, maleic anhydride modified EPM-(1) and EPM-
(3), and the same evaluation was performed for each.

The results are shown in Table-1.

(Examples 15 and 16) The same evaluation as in Example 1 was performed except that the blending ratio of component (A) was changed. The results are shown in Table-1.

(Reference Example 4) Production of epoxy group-containing EPM 100 parts by weight of the EPM used in Reference Example 1 was mixed with 0.5 parts by weight of dicumyl peroxide and 3 parts by weight of glycidyl methacrylate, and the cylinder temperature was set at 200°C. The mixture was kneaded using an extruder to pelletize the epoxy group-containing EPM. From the infrared absorption spectrum, it was confirmed that 1.3% by weight of glycidyl methacrylate was grafted onto EPM. The obtained graft copolymer is referred to as epoxy group-containing EPM.

(Reference Example 5) Production of carboxyl group-containing EPM 1.3 parts by weight of EPM used in Reference Example 1
-bis(tert-butylperoxypropyl)
0.5 part by weight of benzene and 1 part by weight of acrylic acid or methacrylic acid were mixed and kneaded in an extruder set at a cylinder temperature of 220°C to pelletize the carboxyl group-containing EPM. It was confirmed from the infrared absorption spectrum that 0.8% by weight of acrylic or methacrylic acid was grafted onto EPM.

(Example 17) Similar evaluation was performed using an epoxy group-containing EPM instead of the maleic anhydride-modified EPM-(2) used in Example 5. The results are shown in Table-1.

(Example 18) Similar evaluation was performed using a carboxyl group-containing EPM instead of the maleic anhydride-modified EPM (2) used in Example 5. The results are shown in Table-1.

(Reference example 6) High density polyethylene (Mitsubishi Yuka Corporation, BX50A) 10
0 parts, 1.3-bis(tert-butylperoxypropyl)benzene 0.5 parts and maleic anhydride 0
．． 5 parts were mixed and kneaded in an extruder set at a cylinder temperature of 200°C to produce maleic anhydride-modified polyethylene pellets. Quantitative analysis using an infrared absorption spectrum confirmed that 0.3% by weight of maleic anhydride was added. This is called maleic anhydride PE4).

(Reference Example 7) 0.3% by weight of maleic anhydride was prepared in the same manner as in Reference Example 4, except that 100 parts of low-density polyethylene (manufactured by Mitsubishi Yuka ■, 2C-30) was used instead of high-density polyethylene. Added maleic anhydride modified polyethylene pellets were produced. This is called maleic anhydride-modified PE-f2).

(Reference Example 8) 0.3% by weight of 9-maleic anhydride was added in the same manner as in Reference Example 4, except that 100 parts of polypropylene (manufactured by Mitsubishi Yukahata, MA-3) was used instead of high-density polyethylene. Maleic anhydride-modified polypropylene pellets were produced. This is maleic anhydride-modified PP.
It is called.

Examples 19 to 34 Each component having the composition ratio shown in Table 2 was heated at 190°C using a plastomill (manufactured by Toyo Seiki Seisakusho) at 60rpI11.
The mixture was kneaded for minutes to obtain each composition. Table 2: The thermoplastic polyurethane shown in IJ is [Clamilon U3190J
(■Kuraray) is used as high-density polyethylene [B
X50AJ (manufactured by Mitsubishi Yuka) was used as the low density polyethylene, JZC-30J (manufactured by Mitsubishi Yuka) was used as the low density polyethylene, and rMA3J (manufactured by Mitsubishi Yuka) was used as the polypropylene.

Each of the obtained compositions was press-molded, compression-molded test pieces were prepared, and various physical properties were measured. Among each physical property, VIC
AT softening point, 100% tensile stress (M), tensile strength (
TB), elongation at break (EB) 00, and taper wear amount were measured in the same manner as described above, and other physical properties were measured as described below. The results are shown in Table-2.

0 O Transparency Judging by visual inspection of compression molded 1mmmm-t Transparency 20,
Translucent: △, Opaque: × 0 A hot water resistant tensile test piece was immersed in hot water at 70°C for 10 days, and then evaluated by the retention rate (%) when pulled according to JIS K6301.

O Hardness A, based on STM D2240, ShoreD
It was measured with a hardness meter.

○ Weight The 23°C value was determined by the buoyancy method.

O Low temperature impact Izot impact strength (JIS K7110) Notched Izot impact strength was measured at -30°C.

(Comparative Example 1) Instead of the maleic anhydride-modified EPM-(1) used in Example 1, a blend with EPM before modification was evaluated. The results are shown in Table-3. In terms of mechanical strength, heat resistance, and abrasion resistance, better physical property values were obtained when maleic anhydride-modified EPM was used.

(Comparative Example 2) Maleic anhydride modified EP M used in Examples 4 to 12
Similar evaluations were conducted for typical composition ratios using unmodified EPM instead of -(2). The results are shown in Table-3. When using maleic anhydride-modified EPM-(21), better physical property values than unmodified EPM were obtained in terms of TB, VICAT softening point, and wear amount.

(Comparative Example 3) The thermoplastic polyurethane used in the present invention was evaluated. The results are shown in Table-3. According to the present invention, it is possible to achieve low hardness and low elastic modulus, and furthermore, low water absorption and processability are also improved.

(Comparative Example 4) A similar evaluation was conducted using 40 parts by weight of maleic anhydride EPM (2) used in Example 2 with respect to 60 parts by weight of thermoplastic polyurethane. The results are shown in Table-3. In this case, the fluidity of the composition was poor, and a sample whose physical properties could be measured could not be obtained.

(Comparative Example 5) Ethylene-
24 parts by weight of propylene copolymer rubber, maleic anhydride E
Similar evaluations were conducted using 1 part by weight of PM-(2). The results are shown in Table-3. Due to insufficient compatibility between TPU and olefin polymers without functional groups, mechanical strength and
Preferred physical property values of heat resistance were not obtained.

(Comparative Example 6) 79 parts by weight of ethylene-propylene copolymer rubber and maleic anhydride EP per 1 part by weight of thermoplastic polyurethane
Similar evaluations were conducted using 20 parts by weight of M-(2). The results are shown in Table-3. Since the amount of TPU was small, mechanical strength, heat resistance, and abrasion resistance were poor.

Comparative Examples 7 to 20 Compositions were obtained in the same manner as in Examples 9 to 34 of Example 3 using each component in the composition ratio shown in Table 4. The physical properties of each of the obtained compositions were measured in the same manner as in Examples 19-34. The results are shown in Table 4.

In Comparative Examples 7 to 11, in which the amount of component (b) used in the present invention was less than the range of the present invention, the compatibility of components (a) and (c) was insufficient, resulting in poor tensile properties, abrasion properties, and hot water resistance. inferior to

In Comparative Examples 12 to 14, the amount of component (b) used exceeded the range of the present invention, and the fluidity was poor and molding could not be performed.

Comparative Examples 15 to 17 have component (a) below the range of the present invention and are poor in low-temperature impact resistance, while Comparative Examples 18 to 20 in which component (a) exceeds the range of the present invention have poor hot water resistance. inferior to

Blank space below 4 [Effects of the Invention] The composition of the present invention has high strength, high elongation, high softening temperature, and abrasion resistance that cannot be obtained with conventional blends of thermoplastic polyurethane and unmodified olefin polymers. It maintains the superior properties of thermoplastic polyurethanes such as low hardness,
A thermoplastic polymer composition with low modulus flexibility, low water absorption, low density, and low-temperature impact resistance is obtained, and is extremely practical.

Claims (2)

[Claims] (1) Thermoplastic polyurethane (A) 2 to 98% by weight, and olefin polymer (B) having at least one functional group selected from carboxyl group, acid anhydride group, and epoxy group 2 to 28% by weight A thermoplastic polymer composition comprising: (2) Thermoplastic polyurethane (A) 2 to 98% by weight, an olefin polymer (B
) 1 to 35% by weight, and an olefinic polymer (C) having no functional group 1 to 97% by weight.