JP2888044B2 - Modifier for polypropylene resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic polyurethane.
The present invention relates to a polypropylene resin modifier comprising a resin.

[0002]

2. Description of the Related Art Conventionally, polypropylene resin (hereinafter referred to as PP)
The problems described above are that impact resistance at low temperatures is poor due to a high embrittlement temperature, and adhesion is poor due to surface inertness. As a method for solving these problems, a method using a copolymer with ethylene or the like and a method of adding polyisobutylene, diene rubber, or the like have been known.

[0003]

However, the conventional method using a copolymer is a method for improving PP production, and cannot be said to be a simple method. Also, the method of adding a polymer such as polyisobutylene does not include the addition of a compatibilizer.
But it is not technically easy. Although the low-temperature impact resistance can be improved to some extent by adding a usual thermoplastic polyurethane resin (hereinafter abbreviated as TPU), a great effect cannot be obtained because of poor compatibility with PP. An object of the present invention is to provide a useful modifier having excellent compatibility with PP and improving the physical properties of PP.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve such conventional problems, and as a result, have found that a TPU containing a specific polyester polyol in its composition exhibits an excellent modifying effect. And completed the present invention. That is, the present invention provides a number average molecular weight of 500 to 5
000 polyester polyol 100 parts by weight , unsaturated group-containing compound 5 having two or more methyl groups in the molecule
Polyester modified product obtained by reacting 100 parts by weight of a polyisocyanate compound and a chain extender are reacted
Polypropylene made of thermoplastic polyurethane resin obtained
It is a modifier for ren resins .

[0005] The blend of TPU and PP obtained according to the present invention has a uniform dispersion of both components, so that the PP
The brittleness temperature of the resin is reduced , and the adhesion to other resins is also improved. Further , for example, an improvement in adhesion to a urethane paint used as a surface paint is also expected.

The polyester polyol used in the present invention includes a number average molecular weight of 500 used as a reaction partner of a polyisocyanate in the production of TPU.
~ 5000 polyesters, polyesteramides,
Examples thereof include polyetheresters and polycarbonates.

[0007] As polyesters and polyesteramides are produced in a known manner, from a polyhydric alcohol and a polycarboxylic acid, optionally include those obtained by a combination of diamines and aminoalcohols.
Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol,
Examples include methylpentanediol, cyclohexanedimethanol, glycerin, and trimethylolpropane.
Examples of the polycarboxylic acids include succinic acid, adipic acid, sebacic acid, dimer acid, phthalic acid, alkyl phthalates, trimellitic acid, pyromellitic acid, maleic acid, fumaric acid , and itaconic acid. Also,
Those obtained by ring-opening polymerization of cyclic esters such as butyrolactone, valerolactone and caprolactone are also included.

The polyetheresters are the same as the above-mentioned polyesters except that polyetheresterpolyols are used as a part of the polyhydric alcohols used in the above-mentioned polyesters.

As polycarbonates, 1,6-
Polycarbonate diols obtained by transesterification of aliphatic diols or alicyclic diols such as hexanediol and 1,4-cyclohexanedimethanol with dialkyl carbonates , diaryl carbonates, and cyclic carbonates such as ethylene carbonate are exemplified. .

The number average molecular weight of the polyester polyol used in the present invention is from 500 to 5,000 , more preferably from 500 to 3,000. Number average molecular weight of 50
If it is less than 0 , the resulting modifier is not preferred because it has no effect of lowering the embrittlement temperature of PP . Number average molecular weight is 5
If it exceeds 000, the viscosity of the polyester polyol is
It is not preferable because the reaction temperature is too high and the reaction with the unsaturated group-containing compound becomes difficult.

[0011] used in the present invention, the unsaturated group-containing compound having two or more methyl groups in the molecule, for example, acrylic acid, isopropyl alcohol, isobutyl alcohol, neopentyl alcohol, or such as 2-ethylhexanol Esterified product of methacrylic acid,
Examples thereof include any of esterified compounds of any of itaconic acid, maleic acid, and fumaric acid , and methanol, ethanol, isopropyl alcohol, isobutyl alcohol, neopentyl alcohol, and 2-ethylhexanol. The two end fully unsaturated group-containing compound is a methyl group in the molecule, the compatibility with the resulting modifier and PP is undesirably poor Kunar.

The present invention provides a number average molecular weight of 500 to 500.
0 in 100 parts by weight of polyester polyol
Unsaturated group-containing compounds having 2 or more methyl groups 5 to 10
0 parts by weight of the modified polyester obtained by reacting
Obtained by reacting a lysocyanate compound with a chain extender.
Made of thermoplastic polyurethane resin
It is a resin modifier. This modified polyester smell
Te, when the unsaturated group-containing compound is less than 5 parts by weight, to give al
This is not preferred because the compatibility between the modifying agent and PP deteriorates. On the other hand, when the amount exceeds 100 parts by weight , the viscosity of the modified polyester is increased, and the workability is deteriorated.

[0013] Polyester-modified product of the present invention,
It is obtained by reacting a polyester polyol with an unsaturated group-containing compound. This reaction method is not particularly limited , and a usual polymerization method of an ethylenic monomer using a radical initiator or the like can be used. In this reaction, a solvent can be used if necessary. As the solvent, for example, butyl acetate, dioctyl phthalate, dimethylformamide,
Cyclohexane and the like can be mentioned.

[0014] Polyester-modified product of the present invention may be added other polyols. Sunawa <br/> Chi, other polyester polyols described above, polyether polyols, etc. can also be used.

[0015] As the polyisocyanate compound used in the present invention, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylene Li diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, and aromatic consisting of isomers Based diisocyanate, 1,6-hexamethylene diisocyanate,
Examples thereof include aliphatic diisocyanates such as 1,12-dodecane diisocyanate, alicyclic diisocyanates such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. Further, an isocyanate group-terminated compound obtained by reacting these compounds with an active hydrogen group-containing compound,
Alternatively, a reaction of these compounds, for example, a modified isocyanate by a carbodiimidization reaction, and the like can also be mentioned.

The chain extender used in the present invention includes
Ethylene glycol, propanediol, butanediol, hexanediol, neopentyl glycol, 1,
4- bis (beta-hydroxyethyl an ethyl) benzene, glycols such as cyclohexanedimethanol, ethylene diamine, hexamethylene diamine, hydrazine, diamino <br/> di phenyl methane, isophoronediamine, amine such as various amino alcohols and the like No.

The TPU in the present invention is obtained by reacting a modified polyester, a polyisocyanate compound and a chain extender. The charging ratio is such that the molar ratio between the chain extender and the modified polyester is 0.1 to 10, and isocyanate groups of the polyisocyanate compound;
It is preferable that the molar ratio between the chain extender and the active hydrogen groups of the modified polyester be 0.7 to 1.3. In addition, the reaction method, reaction conditions, production facilities, and the like that are usually used in TPU can be used.

Other resins can be added to the modifier of the present invention as needed. As other resins , for example
Acrylonitrile - butadiene - styrene polymers, scan <br/> styrene - acrylonitrile polymers, polyvinyl chloride,
Examples include chlorinated polypropylene, polystyrene, polyacetal, nylon, polyester, polycarbonate, epoxy resin, amino resin, and phenol resin.

The modifier of the present invention may be added as necessary.
Agents can be added . As additives, such as antioxidants, ultraviolet absorbers, heat resistance improving agents, coloring agents, inorganic and organic fillers, plasticizers, lubricants, antistatic agents and reinforcing materials.

Method for blending the modifier of the present invention with PP
Can be melted by twin screw extruder after dry blending
Mixing and the like .

[0021]

EFFECT OF THE INVENTION The modifier for PP of the present invention can be easily
To improve the physical properties of PP .

[0022]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples , but the present invention is not limited thereto. In the examples and comparative examples, "parts" means "parts by weight", and "%" means "% by weight".

In Synthesis Examples 1 to 12 and Tables 1 and 2,
Abbreviations used are as follows: BA-2000: Poly (butylene adipate) polyol hydroxyl value = 56 KOH mg / g Number average molecular weight = 2000 BA-1000: Poly (butylene adipate) polyol hydroxyl value = 110 KOH mg / g Number average molecular weight = 1000 PCL-2000: Poly (caprolactone) Polyol hydroxyl value = 56 KOH mg / g Number average molecular weight = 2000 PEAM-1500: Poly (ethylene adipate malate) Polyol hydroxyl value = 73 KOH mg / g Number average molecular weight = 1500 1,4-BD: 1,4-butanediol MDI: Diphenylmethane Diisocyanate

[ Synthesis of Modified Polyester] Synthesis Example 1 BA-2000 was placed in a 5000 ml separable flask.
2560 parts and heated to 100 ° C. while flowing nitrogen gas.
Heated. In this, 9.0 parts of benzoyl peroxide was dissolved.
440 parts of 2-EHM were dropped from a dropping funnel. Suitable
After the completion, the reaction was carried out for 1 hour, and then at 120 ° C. for 1 hour.
Reaction time to obtain modified polyester MPES-1
Was.

Synthesis Example 2 In the same apparatus as in Synthesis Example 1, 2700 parts of BA-1000 were used.
It was charged and heated to 100 ° C. while flowing nitrogen gas. This
IPM30 in which 6.0 parts of benzoyl peroxide is dissolved
0 parts was dropped from the dropping funnel. One hour after finishing
And then further reacted at 120 ° C for 1 hour.
A modified ester MPES-2 was obtained.

Synthesis Example 3 In the same apparatus as in Synthesis Example 1, PCL-2000 was
Parts and 750 parts of butyl acetate, and flow nitrogen gas.
While heating to 100 ° C. Benzoyl peroxide 2
1200 parts of 2-EHM in which 4 parts were dissolved was dropped from a dropping funnel.
It was dropped. After the completion of the dropwise addition, the reaction is carried out for 1 hour.
After reacting at 120 ° C for 1 hour, gradually reduce the pressure
The butyl was distilled off to obtain a modified polyester MPES-3.
Obtained.

Synthesis Example 4 Poly (ethylene adipate) having a number average molecular weight of 1,000
200 parts of riol and 5 parts of maleic anhydride at 170 ° C. for 5
Heating for an hour gave PEAM-1500. Synthesis Example 1
In a similar device, 1200 parts of PEAM-1500 and
Charge 500 parts of butyl acetate and add 1 part while flowing nitrogen gas.
Heated to 00 ° C. 16 parts of benzoyl peroxide was dissolved in this.
800 parts of the disassembled IPM was dropped from the dropping funnel. drop
After completion of the reaction, the reaction was carried out for 1 hour.
After reacting for 1 hour, the pressure was gradually reduced to remove butyl acetate.
Thus, a modified polyester MPES-4 was obtained. MPES
Table 1 shows compositions (excluding solvents) of -1 to -4.

[0028]

[Table 1]

[ Synthesis of TPU] Synthesis Example 5 1880 MPES-1 was added to a 3.5-ton pressure kneader.
Copies, 245 copies of 1,4-BD and 874 copies of MDI
Charge and heat to 100 ° C to synthesize TPU (PU-1 )
did. This PU-1 was extruded from a CR50-25 type extruder (clear
200-220 ° C using Eight Plastics
And pelletized.

Synthesis Examples 6 to 12 Using a 3.5-ton pressurized kneader,
PU (PU-2 to 8) was synthesized. Then, the synthesis example
1. Pelletization was performed in the same manner. Table 1 shows the composition of PU-1 to PU-8.
It is shown in FIG.

[0031]

[Table 2]

[ Modification of PP] Example 1 30 parts of PU-1 was added to PP (manufactured by Mitsubishi Yuka Co., Ltd., for injection molding).
Grade MA3) for 70 parts by dry blending
The mixture into a PCM45 extruder (Ikegai Iron Works)
The mixture was kneaded at 190 to 210 ° C. and pelletized. This page
The specimen was made into a test piece of 120 × 120 × 2 mm.
For SHV-100 injection molding machine (Yamashiro Seiki Seisakusho)
From 190 to 200 ° C.

Dynamic viscoelasticity measurement of this sheet (TOYOBO
Ludow made Leo vibron, frequency 11Hz, heating rate
The degree of glass transition temperature (Tg) was determined from the
As a result, the temperature was -80 ° C. Graphic weight impact drop
Star (manufactured by Toyo Seiki Seisakusho, drop height 18cm, weight
6.5kg) to perform a falling weight impact test at -10 ° C
Was. The total absorbed energy of this sheet is 1.48 joules.
(Hereinafter abbreviated as J).

Examples 2 to 4 and Comparative Examples 1 to 5 TPU and PP were dry-blended at the ratios shown in Table 3.
Thereafter, a test piece was prepared and a physical property test was performed in the same manner as in Example 1.
Was. Table 3 shows Examples 1 to 4 and Comparative Examples 1 to 5.

[0035]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 23/10-23/14 C08L 75/06 C08G 18/63

Claims (1)

(57) [Claims] 1. A modified polyester obtained by reacting 100 parts by weight of a polyester polyol having a number average molecular weight of 500 to 5,000 with 5 to 100 parts by weight of an unsaturated group-containing compound having two or more methyl groups in the molecule. Thermoplastic obtained by reacting isocyanate compound and chain extender
For Polypropylene Resin Composed of Conductive Polyurethane Resin
Agent .