JPS61171731A - Polycaprolactone amide elastomer - Google Patents

Abstract

PURPOSE:The titled impact-absorbing elastomer suitable especially as a plastic bumper for automobiles, having improved rigidity and impact resistance, comprising a polyamide component and a polycaprolactone component in a specific ratio. CONSTITUTION:(A) 20-90wt% polyamide-forming compound of a nylon salt (e.g., adipic acid-hexamethylene salt, etc.) consisting of 6-12C aminocarboxlic acid (preferably 6-aminocaproic acid (preferably 6-aminocaproic acid, etc.) or 6-12C lactam (preferably caprolactam, etc. or 4-12C dicarboxlic acid and 4-12C diamine is reacted with (B) 4-54C dicarboxylic acid (preferably terephthalic acid, etc.), and (C) 80-10wt% polycaprolactonediol having 200-2,500 average molecular weight or 4,500-100,000 number average molecular weight, to give the aimed elastomer.

Description

Detailed Description of the Invention (Technical Background) The present invention relates to a shock-absorbing polyamide efstomer having excellent rigidity and impact resistance, which is particularly suitable for plastic bumpers for automobiles. The present invention relates to a polycarbonate block tonamide elastomer which has both rigidity and excellent impact absorption and is composed of 20 to 90% by weight of a polyamide component suitable for use in the industry and 80 to 10% by weight of a polycaprolactone component.

In recent years, urethane resins for RIM, modified polypropylene, and polycarbonate have been developed as impact-absorbing resins used for automotive plastics and bumper panels.
It is used as M urethane bumper, modified polycarbonate bumper, and polycarbonate bumper.

However, the RIM urethane bumper has the disadvantage that the manufacturing method is complicated and that the product cost is high because it requires reinforcement from the back side. Modified polypropylene bumpers also have the disadvantage that when the impact strength of the material is increased, the flexural modulus decreases, and therefore metal or plastic reinforcement is required from the back side of the bumper. Furthermore, the modified polypropylene bumper requires a very complicated painting method, which is one of the causes of increased costs. On the other hand, polycarbonate bumpers have high notch sensitivity, which poses a major design problem that requires careful attention to unevenness on the bumper surface. Furthermore, polycarbonate bumpers must be painted to prevent solvent cracks due to the use of solvents such as gasoline, which is one of the causes of increased costs.

(Problems to be Solved by the Invention) Plastic pan bars for automobiles are generally required to have rigidity, impact resistance, weather resistance, heat resistance, paintability, workability, etc. Until now, there have been no materials that satisfy these characteristics. There was nothing.

Regarding rigidity, higher is preferable and rigidity is 10, OO
If O% is below, it is necessary to rub the wall thickness by 6n or more or provide a reinforcing rig on the back side. Regarding impact resistance,
Materials that break brittle are not preferred in terms of safety and energy absorption ability, and materials that break ductile are preferred. Regarding weather resistance, it is preferable that the material does not deteriorate due to the effects of ultraviolet rays, water droplets, temperature changes, etc. Heat resistance: ・Two things are preferable: there is no change in rigidity etc. in an atmosphere of 80°C.

Therefore, the inventors of the present invention conducted intensive studies to obtain a resin suitable for a plastic bumper for automobiles that satisfies the above-mentioned characteristic values, and found that the resin consists of a polyamide component of 20 to 90% by weight and a polycarbonate suspension component of 80 to 10% by weight. We have completed the present invention by discovering that polycarbonate block tonamide elastomer is a resin suitable for automobile plastic bumpers that has both rigidity and impact resistance.

(Structure of the present invention) What is the polycaprolactone amide elastomer used in the present invention? One or more polyamide-forming compounds selected from nylon salts consisting of diamines having a number of 4 to 12.
2) Dicarboxylic acid having 4 to 54 carbon atoms and (3)
Average molecular weight is 200-2.500 or 4,500-10
．． It is a polyester amide obtained by reacting OOO with polycaprolactone diol.

(3) Instead of polycaprolactone diol, an average molecular weight of 200 to 10. OOO polycaprolactone diol 99.9-70% by weight and average molecular weight 200-1
0. It is also possible to use polycaprolactone polyol, which is a mixture with 1 to 30% by weight of polycabrolactone polyol α having three or more OOO functional groups.

The amount of polyamide component in the polycaprolactone amide elastomer of the present invention is preferably 20 to 90% by weight. On the other hand, the amount of polycabrolactone component is preferably 10 to 80% by weight.

This is because if the polyamide component is less than 20% by weight, problems will arise in rigidity, heat resistance, and paintability, while if it is more than 90% by weight, problems will arise in impact resistance.

The polycablock tonamide elastomer of the present invention is prepared by dilution with an initiator, ε-caprolactone or 6-oquinecaproic acid, a polyamide-forming compound, and a dicarboxylic acid. The detailed manufacturing process uses one of the following methods.

A method of producing a polycaprolactone polyol by ring-opening addition of ε-caprolactone to an initiator, and a polycondensation reaction with the polycaprolactone polyol, a polyamide component, and a dicarboxylic acid.

A method for producing a dicarboxylic acid polyamide by reacting a polyamide component with a dicarboxylic acid, and a polycondensation reaction between this dicarboxylic acid polyamide and the above-mentioned polycaprolactone polyol.

q dicarboxylic acid polyamide in the above direction, an initiator and ε
- A method for producing by a ring-opening polycondensation reaction with caprolactone.

0 A method for producing by a ring-opening polycondensation reaction with an initiator, ε-cablocktone, a polyamide component, and a dicarboxylic acid. .

When a polycaprolactone polyol mixture is used, the polyol mixture may be used instead of di-p in the above manufacturing method.

Epsilon-caprolactone, which is a necessary component for producing the polyesteramide of the present invention, is produced industrially by oxidizing dichlorohexanone with peracetic acid by the Bayer-Villiger reaction. Other than ε-cablockone, other lactones such as 4-membered ring gropiolactone can be used in combination with ε-cablockone as long as they do not impair the characteristics of the present invention.

In the present invention, aminocaproic acids having 6 to 12 carbon atoms include 6-aminocaproic acid, 7-aminocaproic acid,
-8-7 minocaglic acid, ω-aminoenanthate, ω-
aminopergonic acid, 11-7 minoundecanoic acid, 12-
Examples include 1-minododecanoic acid, and 6-7-minocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid are particularly preferably used. Also, the number of carbon atoms is 6 to 12
Examples of the lactam include caprolactam, enantholactam, capryllactam, and lauryllactam, with caprolactam and lauryllactam being particularly preferably used. On the other hand, examples of nylon salts consisting of a dicarboxylic acid having a prime number of 4 to 12 and a diamine having 4 to 12 carbon atoms include adipic acid-hexamethylene diamine salt, sebacic acid-hexamethylene diamine salt, isophthalic acid-hexamethylene diamine salt, Examples include terephthalate trimethylhexamethylene diamine salt.

Examples of dicarboxylic acids having 4 to 54 carbon atoms in the present invention include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and diphenyl-4,4'-dicarboxylic acid. , aromatic dicarboxylic acids such as diphenylene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, L2-
Cyclohexanedicarboxylic acid, Synchrohekinru 4.
Examples include alicyclic dicarboxylic acids such as 4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid, and dimer acid. Especially terephthalic acid, isophthalic acid, 1.4
-Cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dodecanedioic acid, and dimer acid are preferably used.

The polycaprolactone diol in the present invention has an average molecular weight of 200 to 2.500 or 4,500 to 10. OOO
are used. This is because if the average molecular weight of polycaprolactone diol is greater than 10.0 (OQ), the lack of flexibility, which is a drawback of high molecular weight polycaprolactone, will occur.

The polycaprolactone polyol in the present invention has an average molecular weight of 200 to 10; polycaprolactone di-/L' of O″DO 99.9 to 70% by weight and three or more functional groups with an average molecular weight of 200 to 10.000. A mixture of 0.1 to 30% by weight of a polycaprolactone polyol having a functional group of 50.1% or more is used.

This is because if the amount is less than 30% by weight, the effect will not be obtained.

be done. However, R is an aromatic hydrocarbon group having 1 to 2 aromatic rings or an alicyclic hydrocarbon group having 4 to 37 carbon atoms, or a saturated or unsaturated aliphatic group having 1 to 30 carbon atoms. group group, or a polyester polyol residue with an average molecular weight of 200 to 6000, or an average molecular fi20
0 to 6000 boria〃kylene glycol residues.

It is a compound represented by

Examples of specific initiators include resorcinol, pyrocatechol, hydroquinone, pyrogallol, phloroglunon, benzene tateol, bisphenol-A, bisphenol-F and their ethylene oxide adducts, dimethylolbenzene, cyclohexane dimetatool, tris( 2-Hydroquinethyl) isonanurate ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2-methyl, 3-propylene glycol, neo Pentyl glycol, 1.5-bentanediol, glycerin, trimethylolpropane, 1,6-hexanediol, pentaerythritol, sorbitol, glucose,
Funosaccharide, dicarboxylic acid components such as terephthalic acid, isophthalic acid, adipic acid, sepacic acid, undecanniic acid, and dodecanniic acid, and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, neo A polyester polyol with an average molecular weight of 200 to 6,000 formed from pentyl glycol, 1,5-bentanediol, 1,6-hexanediol, and a polyolefin component such as trimethylolpropane, glycerin, pentaerythritol, and sorbitol; Examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, mallock or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc. with an average molecular weight of 200 to 6,000.

When a polyol mixture is used as (3), a compound represented by the following general formula is used as an initiator.

R(-OH) e However, R is an aromatic hydrocarbon group having 1 to 2 aromatic rings or an alicyclic hydrocarbon group having 4 to 37 carbon atoms. Saturated or unsaturated aliphatic group having a carbon number of 11 to 30" or an average molecular weight of 200 to 6000
polyester polyol-IV residues, or average molecular weight 2
00 to 6000 polyalkylene glycol residues. Moreover, e is an integer of 2 to 8.

The specific compounds are as follows.

-・+su,. , resol 7, pyrocatechol, hydroquinone, pyrogallol, phlorogrin, benzenetriol, bisphenol ratio, bisphenol-F and their ethylene oxide adducts, dimethylolbenzene, cyclohexane dimetatool, tris(2-hydroxyethyl)isocyanurate, ethylene glycol,
Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1゜4-
Butanediol, 1,3-butanediol, 2-methyI
v-1,3-propylene glycol, neopentyl glycol, 115-bentanediol, glycerin, trimethylolpropane, 1,6-hexanedio-M1 pentaerythritol, sorbitol, glucose, sila sugar,
Dicarboxylic acid components such as oyohiterephthalic acid, isophthalic acid, adipic acid, sepacic acid, undecanniic acid, dodecanniic acid, ethylene glycol, diethylene glycol-M,
Triethylene glycol, propylene glycol, L4
-Butanediol, neopentyl glycol, 1.5-
An average molecule formed from polyol components such as bentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, and Tsuruhito-p! 200-6000 polyester polyol and average molecular weight 200-6. Examples include OOO polyethylene glycol, holiderobylene glycol, polytetramethylene glycol, block or random copolymers of ethylene oxintotopropylene oxide, and block or random copolymers of ethylene oxide and tetrahydrofuran.

The ring-opening addition reaction of ε-cablocktone to the hydroxyl group of the initiator is carried out at 100 to 230°C. Further, it is preferable to use a catalyst in this reaction. Examples of catalysts include titanium compounds such as tetramethyl titanate, tetrapro'Ktv titanate, and tetraethyl titanate, organic tin compounds such as tin octyl oxide, dibutyltin oxide, and dibutyltin dilaurate, as well as stannous chloride and bromide. Tin halide compounds such as stannous and stannous iodide can be used. The amount used is α01 to 1000 ppm, preferably α2 to 500 ppm.

Further, 6-oxycaproic acid may be used in place of ε-caprolactone. The polycondensation reaction in the present invention may be carried out by a conventional method.

That is, the polycondensation reaction is carried out under a high vacuum of 5 nHf or less, preferably taut or less, while stirring in the presence of a catalyst.
The reaction temperature is 20-280°C. The ratio of levoxy groups, amino groups and hydroxyl groups of the polyamide component, cicafreponic acid and aliphatic polyester is 0.95≦(C
OOH)/((N)+(OH))≦105, it is important to carry out the polycondensation reaction in combination in the range of 105 to produce a high degree of polymerization polycaprolactone amide elastomer with excellent physical properties is necessary.

In addition, in the polycondensation reaction, tetramethyl titanate,
Tetraisopropyl titanate.

Tetraalkyl titanates such as tetrabutyl titanate, tetra-2-ethyl hexyl titanate, tetraalkyl titanate, tetrahexadodecyl titanate,
Titanium-based catalysts such as potassium titanium oxalate, tin-based catalysts such as dibutyltin oxide, digtyltin dilaurate, motuptyltin oxide, zirconium tetra-M oxide catalysts such as silconium tetrabutoxide and zirconium isopropoxide, and hafnium tetra Hafnium tetraalkoxide catalysts such as ethoxide and lead catalysts such as lead acetate are preferably used.

Furthermore, a nylon 12 homopolymer or a relatively small amount of a plasticizer may be added to the polycaprolactone amide elastomer to the extent that the aforementioned desirable properties are not lost.

(Examples) The present invention will be explained below with reference to Examples, but the present invention is not limited thereby.

Note that the numbers in the middle part of the example mean parts by weight.

Example 1 A polycaprolactone amide elastomer consisting of about 48 parts of 12-aminododecanoic acid, about 6 parts of dodecanedioic acid, and about 50 parts of polycaprolactone diol having a hydroxyl value of 112.0 was vacuum-dried to have a cross section as shown in FIG. Bumper (front thickness ζ = 3. OW, back lip thickness t, =
4 [, body height 11 = l 5 Q tz.

Body depth b = 80 cod, rig length C = 3Q wx.

Lip spacing d=25ff%15'=65fi, moment of inertia 60XiO'W'), stay spacing 62 (
The maximum amount of deformation in the injection molding experiment using a mold with a shape of 11 is that of the front bumper.

Example 2 About 63 parts of 12-aminododecanoic acid, about 5 parts of adipic acid,
A polycaprolactone amide elastomer made of about 32 parts of polycaprolactone diol having a hydroxyl value of 112.0 was injection molded in the same manner as in Example 1 and subjected to a pendulum impact test.

Comparative Example 1 Nylon-6 obtained by melt polymerizing ε--hf rolactam
was injection molded in the same manner as in Example 1, and a pendulum impact test was conducted.

The results of these impact tests are shown in Table 1.

Table 1 □ (Effects) From the results in Table 1, it can be seen that the polycaprolactone amide elastomer of the present invention has extremely excellent impact resistance at room temperature and low temperature.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing an example of a bumper according to the present invention. (Explained in No. 7) *Q子C--1--Rib Kating d, e-m-sama 5-view patent applicant DaishichiM Chemical Industry Co., Ltd. Yuu 1 Drawing procedure amendment (voluntary) Patent dated February Z7, 1986 Director General Uga Michibe L Display of the case 1985 Patent Application No. 10303 2 Name of the invention Polycaprolactoneamide elastomer 3, Relationship with the person making the amendment Case Detailed description of the invention in the patent applicant's specification Tortoise Contents of correction (1) Correct "dichlorohexanone" in the 5th to 6th lines from the top of the 7th X to "cyclohexanone" K. (2) From the 11th purchase, in the 4th line, "Cyanurate Ethylene Glyco-μ" is corrected to "Cyanurate, Ethylene Glycol".

Claims (1)

[Claims] A polycaprolactone amide elastomer having excellent impact absorption and comprising 20 to 90% by weight of a polyamide component and 80 to 10% by weight of a polycaprolactone component.