JPH0680871A - Thermoplastic polyurethane resin composition and article using the same - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition capable of providing moldings excellent in impact resistance at extremely low temperatures. CONSTITUTION:The objective thermoplastic resin composition is obtained by melt kneading a thermoplastic polyurethane resin composed of epsilon-caprolactone- based lactone polyester/1,4-butandiol/diphenylmethane diisocyanate with a maleic anhydride-graft ethylene-butene-1 copolymer and/or glycidyl methacrylate-graft ethylene-butene-1 copolymer and a thermoplastic polyester resin composed of poly(tetramethylene ether)glycol/1,4-butandiol/terephthalic acid. Thereby, this thermoplastic resin composition is capable of providing moldings, good in not only impact strength at extremely low temperatures but also compatibility in molding and excellent in tensile strength at high temperatures.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyurethane resin composition having excellent impact resistance, particularly cold impact resistance, and excellent adhesion to RIM urethane and the like, which is suitable as a vehicle interior or exterior member. Is.

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 2-120358 discloses a thermoplastic resin composition obtained by melt-kneading a thermoplastic polyurethane resin and a modified polyolefin resin.

The thermoplastic polyurethane resin and the modified polyolefin resin are compatible with each other to some extent, but the extent is not yet satisfactory. Therefore, even if they are used as a mixture, they are expected. There is a drawback that the strength and elongation cannot be obtained as much as there is. Moreover, the composition described above had insufficient impact resistance at extremely low temperatures.

Therefore, the present inventors have
Upon intensive study in view of the above situation, when a thermoplastic polyester resin is used in combination with a conventional composition, the compatibility between the thermoplastic polyurethane resin and the modified polyolefin resin is improved, and only good strength and elongation can be obtained. However, they have found that they also have excellent impact resistance at extremely low temperatures, and have completed the present invention. That is, the present invention provides a thermoplastic polyurethane resin composition comprising a thermoplastic polyurethane resin (A), a modified polyolefin resin (B) and a thermoplastic polyester resin (C), and an article formed by molding the thermoplastic polyurethane resin composition. It is provided.

[Structure] The thermoplastic polyurethane resin (A) used in the present invention may be any known and commonly used one, but preferably has a hardness (JIS) at 25 ° C. of 80 to 100, particularly preferably 89 to 99, Tensile strength is preferably 200
kg / cm ² or more, particularly preferably 300 to 500 kg / cm ² ,
The breaking elongation is preferably 300% or more, particularly preferably 4
A material having a physical property of 00% or more is used.

The resin (A) can be easily produced by reacting a polyhydroxyl compound (polyol component) and a polyisocyanate compound (isocyanate component) as essential components.

As the polyhydroxyl compound for obtaining the resin (A), for example, various polyester polyols and / or polyether polyols used for the production of general urethane compounds can be mentioned.

Examples of the polyester polyols mentioned here include condensates of polyhydric alcohols and polybasic carboxylic acids, and the polyhydric alcohols used therein are, for example, ethylene glycol, propylene glycol, butanediol, diethylene glycol. , Glycerin, hexanetriol, trimethylolpropane and the like, and the polybasic carboxylic acid, for example, adipic acid, glutaric acid, azelaic acid, fumaric acid,
Maleic acid, phthalic acid, terephthalic acid, dimer acid, pyromellitic acid and the like can be mentioned. Further, as a condensate of hydroxycarboxylic acid and polyhydric alcohol, castor oil, or a reaction product of castor oil and ethylene glycol, propylene glycol or the like is also useful. Further, as the polyester polyol, lactone-based polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone can also be used. The lactone-based polyester polyols include ε-caprolactone, δ-valerolactone, β-methyl-δ and the polyhydric alcohols described above.
Any one obtained by addition-polymerizing one kind or two or more kinds such as valerolactone can be used.

As the polyether polyol, for example, one kind or two or more kinds of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran are used, and as the compound having two or more active hydrogens, for example, the polyhydric compounds described above. In addition to alcohols and polybasic carboxylic acids, amines such as ethylenediamine and hexamethylenediamine, alkanolamines such as ethanolamine and propanolamine,
Polyhydric phenols such as resorcin, bisphenol,
Castor oil and the like can be mentioned.

As the polyhydroxyl compound, one kind or two or more kinds of a polyester polyol and a polyether polyol are used, and further a low molecular weight polyhydroxy compound such as the above-mentioned polyhydric alcohol is used as a chain extender. good.

The polyisocyanate compound used to obtain the resin (A) is a compound having two or more isocyanate groups in the molecule, and various compounds commonly used in the production of polyurethane resins can be used. For example, tolylene diene Aromatic polyisocyanate compounds such as isocyanate, diphenylmethane diisocyanate, dianidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, bis (diisocyanate tolyl) phenylmethane, polymethylene polyphenyl polyisocyanate, aliphatic or alicyclic compounds Examples of the polyisocyanate compound include isophorone diisocyanate, dicyclohexylmethane diisocyanate (hydrogenated diphenylmethane diisocyanate), and hexamethylene diisocyanate. Xylylene diisocyanate, hydrogenated tolylene diisocyanate, isopropylidene bis (cyclohexyl isocyanate) and the like.

The polyisocyanate compound used in the present invention may be a combination of two or more kinds of polyisocyanate compounds, in particular an aliphatic or alicyclic polyisocyanate compound and an aromatic polyisocyanate compound. Good.

As the polyol component of the polyurethane resin, all of the above-mentioned polyhydroxyl compounds used for producing the isocyanate group-containing urethane prepolymer can be used. That is, one or more of the above polyester polyols and polyether polyols can be used. Also, a low molecular weight polyhydroxyl compound such as the above-mentioned polyhydric alcohol can be used together as a polyol component.

As the resin (A), a lactone polyester polyol and / or a poly (alkylene ether) glycol having an alkylene ether bond having 4 or more carbon atoms as a repeating unit is reacted with an aromatic polyisocyanate as an essential component. Thermoplastic polyurethane resins are preferred.

The modified polyolefin resin (B) used in the present invention is a carboxyl group-containing olefin copolymer and / or an epoxy group-containing olefin copolymer. These include, for example, a polyolefin resin containing polymerized units of ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated polycarboxylic anhydride, or polymerized units of epoxy group-containing ethylenically unsaturated monomer. Is.

The carboxyl group-containing olefin copolymer contains at least 50 mol%, preferably 70 mol% or more of 1-olefin, based on 100 mol% of the total monomers constituting the carboxyl group-containing olefin copolymer. Is preferred. Examples of the 1-olefin include ethylene, propylene, butene-1, isobutene, pentene-1, hexene-1, decene-1,4-methylbutene-1,4-methylpentene-1,4,4-dimethylpentene-1, vinylcyclohexane, styrene. , Α-methylstyrene, styrene substituted with a secondary alkyl substituent, or a compound similar thereto, and the above olefins may be mixed and used.

The polyolefin resin before modification is preferably ethylene-butene-1 copolymer, ethylene-propylene copolymer, or polypropylene. Examples of commercially available polyolefin resins before modification include Tuffmer A4085, Tuffmer A4090, and Tuffmer A200.
90 etc. Toughmer A series [ethylene-butene-1 copolymer, Mitsui Petrochemical Industry Co., Ltd. product] and Tuffmer P0
280, Tuffmer P0480, Tuffmer P0680, Tuffmer P0880, and other Tuffmer P series [ethylene-butene-1 copolymer, Mitsui Petrochemical Co., Ltd. product].

The carboxyl group-containing olefin copolymer may be obtained by directly copolymerizing an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated polycarboxylic acid anhydride with the above olefin. It can be produced in advance by a method such as graft copolymerization with an ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated polycarboxylic acid anhydride, which has been obtained in advance. The carboxyl group-containing olefin copolymer is preferably the one obtained by the latter method.

Examples of the acid component used to obtain the carboxyl group-containing olefin copolymer include acrylic acid, methacrylic acid and (maleic anhydride), fumaric acid, and monoesters of the above carboxylic acids. Can include acrylic acid, methacrylic acid and (anhydrous) maleic acid. Among them, (anhydrous) maleic acid is particularly preferable because a sufficient acid modification effect can be obtained by adding a small amount as compared with other acids.

Suitable carboxyl group-containing olefin copolymers include (anhydrous) maleic acid-grafted ethylene-butene-1 copolymers, (anhydrous) maleic acid-grafted ethylene-propylene copolymers, (anhydrous). Examples thereof include polypropylene grafted with maleic acid.

The epoxy group-containing olefin copolymer may be obtained by directly copolymerizing the epoxy group-containing ethylenically unsaturated monomer and the above-mentioned olefin, but usually a polyolefin resin is obtained in advance, and an epoxy group is added to the polyolefin resin. It can be produced by a method such as graft copolymerization of the contained ethylenically unsaturated monomer. As the epoxy group-containing olefin copolymer, the one obtained by the latter method is preferable.

The epoxy group-containing ethylenically unsaturated monomer used here is a glycidyl ester of α, β-ethylenically unsaturated carboxylic acid, and examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid and the like. Of these, glycidyl methacrylate is preferably used.

Such modified polyolefin resin (B)
Is 0.01 to 20% by weight, particularly 0.0 to 20% by weight, with these monomers having a carboxyl group or an epoxy group as a constituent component.
It is preferably contained in the range of 5 to 5% by weight.

As the modified polyolefin resin used in the composition of the present invention, a carboxyl group-modified polyolefin resin and an epoxy-modified polyolefin resin may be used alone or in combination of two or more kinds at any ratio.

Thermoplastic polyester resin (C) of the present invention
As the material, any of known materials can be used, but the hardness (JIS) at 25 ° C. is preferably 85 to 100, particularly preferably 90 to 98, and the tensile strength is preferably 150 k.
g / cm ² , particularly preferably 250 to 400 kg / c
Those having a m ² and breaking strength of preferably 300% or more, particularly preferably 400% or more can be used.

The resin (C) can be easily obtained, for example, by reacting a polyhydroxy compound (polyol component) with a polycarboxyl compound (polybasic carboxylic acid component). Examples of the polyhydroxy compound used for obtaining the resin (C) include various polyester polyols and / or polyether polyols used in the production of general urethane compounds and the production of polyester elastomer compounds. As the polyhydroxyl compound, one kind or two or more kinds of polyester polyol and polyether may be used, and a low molecular weight polyhydroxy compound such as the above-mentioned polyhydric alcohol may be used together as a chain extender.

As the polycarboxyl compound, any publicly known and conventional one can be used, but it is preferable to use an aromatic polycarboxyl compound. Examples of the aromatic polycarboxyl compound include phthalic acid, isophthalic acid, terephthalic acid and the like.

The resin (C) is preferably a thermoplastic polyester resin obtained by reacting a poly (alkylene ether) glycol having an alkylene ether bond having 4 or more carbon atoms as a repeating unit with an aromatic polycarboxylic acid as an essential component. . The mixing ratio of the resins (A) to (C) is not particularly limited, but is usually the modified polyolefin resin (B) per 100 parts by weight of the total of the thermoplastic polyurethane resin (A) and the thermoplastic polyester resin (C). 0.1 to 49.5 parts by weight may be used.

The weight ratio of the thermoplastic polyurethane resin (A) to the thermoplastic polyester resin (C) is usually 9
It is 9.50 / 0.50-50.05 / 49.95.
Among them, the weight ratio of the thermoplastic polyurethane resin (A) and the thermoplastic polyester resin (C) is 99.50 /
0.50 to 50.05 / 49.95, and the modified polyolefin resin (B) is added in an amount of 0.1 to 49.50 parts per 100 parts by weight of the thermoplastic polyurethane resin (A) and the thermoplastic polyester resin (C). It is common to use 5 parts by weight.

When the blending ratio of each of the resins (A) to (C) of the composition of the present invention is expressed as an internal ratio, when the total weight of these three components is 100 parts by weight, it is usually a thermoplastic polyurethane resin. (A) 99.4 to 50 parts by weight, modified polyolefin resin (B) 0.1 to 49.5 parts by weight,
It is 0.5 to 49.9 parts by weight (weight ratio) of the thermoplastic polyester resin (C).

Incidentally, the larger the amount of the polyester elastomer resin added, the lower the adhesiveness, and the larger the amount of the modified polyolefin resin, the softer the resin tends to become, and the heat resistance and the adhesiveness tend to lower. It is important to properly determine the addition amount according to the purpose.

In the polyurethane resin composition of the present invention, if necessary, a small amount of a releasing agent, a coupling agent, a coloring agent, a lubricant, a weathering stabilizer, a foaming agent, a rust preventive agent, an opacifying agent, an antibacterial agent,
You may add additives, such as a filler.

When preparing the composition of the present invention,
Thermoplastic resins or elastomers other than the resins (A) to (C), such as polyvinyl chloride, ethylene-vinyl acetate copolymer, styrene elastomer, polybutadiene, vinyl chloride elastomer, acrylic polymer, without departing from the object of the present invention. It is also possible to use polyamide, polyimide, polyamideimide, polyphenylene sulfide, etc. in combination.

The thermoplastic resin composition of the present invention can be prepared by various known methods. Examples of the preparation method include a method in which the raw materials are uniformly mixed in advance with a mixing device such as a tumbler or a Henschel mixer, and then supplied to a single-screw or twin-screw extruder and melt-kneaded, and then prepared as pellets. .

The thermoplastic polyurethane resin composition of the present invention has heat resistance and impact resistance without losing the excellent characteristics inherent to the thermoplastic polyurethane resin such as tensile strength, elongation at break, cold resistance and abrasion resistance. , Especially improved cold shock resistance,
Excellent adhesion with RIM urethane. Therefore, the interior and exterior members of the vehicle obtained by molding the polyurethane resin composition of the present invention are extremely practical.

Like the conventional thermoplastic polyurethane resin, the composition of the present invention is used for various molded articles using various thermoforming materials such as tubes, rolls, dust covers, packings, industrial belts, films, shoe soles, and the like. It can be used for ski parts, wire coatings, automobile parts, air bag pad materials, bumper molding materials, etc.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. still,
Parts in the examples and comparative examples mean parts by weight.

Reference Example 1 [Production of Thermoplastic Polyurethane Resin (A)] Lactone-based polyester obtained by ring-opening polymerization of ε-caprolactone (number average molecular weight of about 2000) / 1,4-butanediol / diphenylmethane diisocyanate = 46/1
Polymerization was performed at 2/42 (weight ratio) to obtain a thermoplastic polyurethane resin (a). This resin (a) has a hardness (JI
S A) 99 °, tensile strength 470 kg / cm ² , breaking elongation 450%.

Reference Example 2 [Production of Thermoplastic Polyurethane Resin (A)] Poly (tetramethylene ether) glycol obtained by ring-opening polymerization of tetrahydrofuran (number average molecular weight of about 1000)
/ 1,4-butanediol / diphenylmethane diisocyanate = 45/11/48 (weight ratio) was polymerized to obtain a thermoplastic polyurethane resin (b). This resin (b) has a hardness (JIS A) of 98 ° and a tensile strength of 44.
It was 0 kg / cm ² and the breaking elongation was 470%.

Reference Example 3 (Production of Carboxyl Group-Containing Olefin Copolymer) Tufmer A4090 [Ethylene-Butene-1 Copolymer manufactured by Mitsui Petrochemical Co., Ltd.] 100 parts 1,3-bis (tert-butylperoxy) 0.5 parts of propyl) benzene and 1 part of maleic anhydride were uniformly mixed. Then, the mixture was kneaded with an extruder set to a cylinder temperature of 220 ° C. and pelletized to obtain a carboxyl group-containing olefin copolymer.
When the amount of maleic anhydride grafted was measured by infrared spectrum, the olefin copolymer was found to be ethylene-butene-1.
It was confirmed that 0.75 part of maleic anhydride was grafted to 100 parts of the copolymer. This is referred to as a copolymer (I).

Reference Example 4 (Production of Epoxy Group-Containing Olefin Copolymer) 100 parts of Tufmer A 4090, 0.5 part of dicumyl peroxide and 2 parts of glycidyl methacrylate were uniformly mixed. Then, the mixture was kneaded with an extruder having a cylinder temperature set to 200 ° C. and pelletized to obtain an epoxy group-containing olefin copolymer. When the graft amount of glycidyl methacrylate was measured with a hydrochloric acid-methyl ethyl ketone solution, the olefin copolymer was found to be grafted with 1.25 parts by weight of glycidyl methacrylate of methacrylate per 100 parts of ethylene-butene-1 copolymer. It turned out that This is referred to as a copolymer (II).

Reference Example 5 [Production of Thermoplastic Polyester Resin (C)] Poly (tetramethylene ether) glycol obtained by ring-opening polymerization of tetrahydrofuran (number average molecular weight of about 1000)
/ 1,4-butanediol / terephthalic acid = 40/1
It was condensed at 2/48 (weight ratio) to obtain a thermoplastic polyester resin (a). This resin (a) has a hardness (JI
S A) 95 °, tensile strength 400 kg / cm ² , breaking elongation 400%.

Examples 1 and 2 and Comparative Examples 1 to 3 The thermoplastic polyurethane resin (a) obtained in Reference Example 1 and Pandex T-5167 (thermoplastic polyurethane resin manufactured by Dainippon Ink and Chemicals, Inc.), Reference Example The copolymers (I) and (II) obtained in 3 and 4 and the thermoplastic polyester resin obtained in Reference Example 5 were blended in the proportions shown in Table 1 using a 50 mm extruder at 190 to 200 ° C
Was kneaded and pelletized.

The pellets were injection molded (3 ounce 60 ounces).
A sheet having a thickness of 2 mm and a sheet having a thickness of 3 mm were formed with a ton-type clamping machine to obtain a test piece. Using this test piece, Izod impact strength, tensile strength, hardness and elongation, compatibility,
Adhesion was measured (JIS K-7311 and ASTM
According to D-256. ). The test results are shown in Table 1.

Specific measurement methods and evaluation criteria for some evaluation items are as follows. * 1) Izod impact test: Izod impact test was performed at 0 ° C and -40 ° C. If the test piece was not destroyed, it was designated as “NB”. If it was destroyed, the strength was based on the weight of the weight at the time of fracture. The calculated value was displayed.

* 2) Compatibility Evaluation Criteria (Presence of Poor Poor Phenomenon): The compatibility was judged to be better by visually observing the surface condition of the extruded sample by an extruder. ◎ Excellent ○ Good △ Somewhat good × Bad

* 3) Criteria for evaluating compatibility (presence or absence of phase separation phenomenon): Compatibility is better when pellets produced by an extruder are injection-molded into a sheet and the surface condition is visually observed. It was judged. ◎ Excellent ○ Good △ Somewhat good × Bad

* 4) Adhesion Evaluation Criteria: Adhesion with RIM urethane was evaluated by setting a test piece in a mold, injecting RIM urethane stock solution, foaming and molding, and then peeling off the adhesion surface. ◎ Excellent ○ Good △ Somewhat good × Bad

* 5) Adhesion evaluation criteria: For adhesion with ABS, set a test piece in a mold and
After the BS resin was injected and molded, the adhesive surface was peeled off and evaluated. ◎ Excellent ○ Good △ Somewhat good × Bad

[0044]

[Table 1]

As can be seen from Table 1, the composition of the present invention further containing a thermoplastic polyester resin has an extremely low temperature (-40 ° C.) as compared with a conventional composition comprising only a thermoplastic polyurethane resin and a modified polyolefin resin. It is understood that not only the impact strength in ()) is particularly excellent, but also the compatibility during molding is good and the tensile strength at high temperature is also excellent.

Examples 2 to 6 Thermoplastic polyurethane resin (a) obtained in Reference Examples 1 and 2
To (b), the copolymers (I) and (II) obtained in Reference Examples 3 and 4, and the thermoplastic polyester resin obtained in Reference Example 5 at the ratios shown in Tables 2 and 3, respectively. The compounded material was pelletized in the same manner as in Example 1 and injection-molded,
Physical properties were measured for the same evaluation items. This result is second
The results are shown in Table 3 and Table 3.

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

Since the composition of the present invention comprises a thermoplastic polyester resin in combination with a conventional composition comprising a thermoplastic polyurethane resin and a modified polyolefin resin, the composition of the thermoplastic polyurethane resin and the modified polyolefin resin is Not only the solubility is further improved and the impact resistance at cryogenic temperature is also excellent, but also a particularly remarkable effect is obtained in that better strength and elongation can be obtained.

Claims (15)

[Claims] 1. A thermoplastic polyurethane resin composition comprising a thermoplastic polyurethane resin (A), a modified polyolefin resin (B) and a thermoplastic polyester resin (C). 2. A blending ratio of the respective resins (A) to (C) of the composition is such that the thermoplastic polyurethane resin (A) is 99.4.
~ 50 parts, modified polyolefin resin (B) 0.1-4
9.5 parts, thermoplastic polyester resin (C) 0.5 to 4
The thermoplastic polyurethane resin composition according to claim 1, which is 9.9 parts (weight ratio). 3. The modified polyolefin resin (B) is contained in an amount of 0.1 to 49.5 per 100 parts by weight of the total amount of the thermoplastic polyurethane resin (A) and the thermoplastic polyester resin (C).
The thermoplastic polyurethane resin composition according to claim 1, which is used in parts by weight. 4. The weight ratio of the thermoplastic polyurethane resin (A) to the thermoplastic polyester resin (C) is 99.50.
The thermoplastic polyurethane resin composition according to claim 1, which is /0.50 to 50.05 / 49.95. 5. A thermoplastic polyurethane resin (A) and a thermoplastic polyester resin (C) in a weight ratio of 99.50.
/0.50 to 50.05 / 49.95, and 0.1 to 100 parts by weight of the total amount of the thermoplastic polyurethane resin (A) and the thermoplastic polyester resin (C). The thermoplastic polyurethane resin composition according to claim 1, which is used in an amount of 49.5 parts by weight. 6. The thermoplastic polyurethane resin (A) has a hardness (JIS A) of 80 to 100 ° and a tensile strength of 200 kg /
The thermoplastic polyurethane resin composition according to claim 1, which has physical properties of cm ² or more and elongation at break of 300% or more. 7. The thermoplastic polyurethane resin composition according to claim 1, wherein the modified polyolefin resin (B) comprises a olefin polymer containing a carboxyl group and / or an epoxy group. 8. A thermoplastic polyester elastomer resin (C) having a hardness (JIS) of 85 to 100 ° and a tensile strength of 1
The thermoplastic polyurethane resin composition according to claim 1, which has physical properties of 50 kg / cm ² or more and elongation at break of 300% or more. 9. The thermoplastic polyurethane resin composition according to claim 1, wherein the modified polyolefin resin is a modified polypropyl and / or modified ethylene propylene copolymer. 10. An extrusion-molded article or an injection-molded article comprising the thermoplastic polyurethane resin composition according to claim 1. 11. A vehicle part or an electric / electronic part and / or a machine / industrial part having excellent impact resistance, which is formed by using the molded product according to claim 10. 12. A RIM comprising the molded article according to claim 10.
Two-color molded product with excellent adhesion to urethane. 13. A two-color molded product, which is obtained by using the molded product of claim 10 and has excellent adhesiveness to other resins. 14. A vehicle interior or exterior component obtained from claim 12 or claim 13. 15. The thermoplastic polyurethane resin (A) essentially comprises a lactone polyester polyol and / or a poly (alkylene ether) glycol having an alkylene ether bond having 4 or more carbon atoms as a repeating unit, and an aromatic polyisocyanate. A thermoplastic polyurethane resin reacted as a component, and a thermoplastic polyester resin (C) comprises a poly (alkylene ether) glycol having an alkylene ether bond having 4 or more carbon atoms as a repeating unit and an aromatic polycarboxylic acid. The thermoplastic polyurethane resin composition according to claim 1, which is a reacted thermoplastic polyester resin as an essential component.