JPS58154723A - Copolyamide resin - Google Patents

Abstract

PURPOSE:A copolyamide resin low in water absorption and excellent in dimensional stability, heat stability, etc., prepared by copolymerizing a polyamide component having specified repeating units with a plyolefin component having functional groups such as carboxyl groups on both terminals. CONSTITUTION:99-5pts.wt. polyamide component having at least one kind of a repeating unit selected from the group consisting of repeating units of formulaI(wherein n is 5-11), and of formula II(wherein X is CmH2m, wherein m is 6-12, isophorone, phenylene or cyclohexylene, and Y is ClH2l wherein l is 4- 10, phenylene or cyclohdexylene) is copolymerized with 1-95pts.wt. polyolefin component, average MW of 500-10,000, having carboxyl, amino or hydroxyl groups on both terminals (e.g., a polymer prepared by terminating a polybutadiene formed by living polymerization with an epoxy compound to introduce hydroxyl groups into the terminals and hydrogenating the product) with the aid of a titanium catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel low water absorption copolyamide resin.

As is well known, polyamide resin is widely used in a wide range of applications including fibers, but due to its structure with adhesion, it inherently has a high water absorption rate and has excellent dimensional stability. is inferior to 9〉,
It has the disadvantage that physical properties such as electrical characteristics change significantly depending on humidity. For example, polyamide resin has a very clear melting point due to its direct dependence on impedance oil and crystalline bird molecules, and can be used as a temperature fuse, making it possible to make electric blankets and electric carpets. , in such applications, the impedance of polyamide resin is 3! It is necessary to be unaffected by Therefore, among polyamide resins, nylon 11. Although nylon 12 is used in such applications, h is still affected by m degrees, and therefore has not achieved sufficiently satisfactory performance.

This product is a new copolymerized polyamide that improves the water absorption, which is a drawback of bolyamide resin, and has the horizontal properties, machinability, and flexibility that bolyamide resin has. Our goal is to provide resin.

That is, the present invention has 99 to 5 parts by weight of a polyamide polymer component having at least one type of repeating unit represented by the following general formula (1) or (2), and both terminals are a carboxylic acid group, an amino group, or a hydroxyl group. (average molecular weight 500-10,000 K)
11th 1st 747th place 1~? 1 part by weight of a novel copolymerized polyamide resin -Ml(OllR)nGo -(1) (wherein, n is an integer of s to 11) -MHXMI100YOO-(1) (wherein, !,, (m is 4~11011I
i) represents an isophorone group, a phenylene group or a 7-chlorohexylene group;
Regarding K.

The above 〇-General formula 1 constituting the copolymerized polyamide of the present invention
) or (2), monomers constituting the boriaod polymer component having one or more types of repeating units include, for example, those corresponding to (1) 2 include caprolactam,
Examples include lauryl lactam, 11-unundecanoic acid, 12-annododecanoic acid, etc., and examples of t corresponding to (2) include hextmetele/adipate, hexmetelet, etc.
(Hehe! In addition to methylene dodeca-densate, etc., diamine salts of dibasic acids with a radical such as terephthalic acid and cyclohexane dicarboxylic acid, dibasic acid salts of diamines such as phenylene diamine, cyclohexane diamine, and isophorone diamine, etc.) Furthermore, the polyolefin having carboxylic acid groups, amino groups or hydroxyl groups at both ends, which is the polyolefin component constituting the copolyamide of the present invention, can be obtained, for example, by radical polymerization from one or more olefin polymers. In order to introduce a functional group such as a carboxylic acid group, an alkyl group, or a hydroxyl group at both ends of the car, the polymerization conditions such as temperature and pressure, as well as the polymerization agent and solvent, must be carefully controlled. .

The above-mentioned polyolefin component of the present invention may be linearly polymerized by introducing a nine-functional group selected from a carboxylic acid group, an amino group, or a hydroxyl group at the end of the polymer having two or more double bonds. This can also be obtained by adding a large amount of water to this. For example, by living polymerizing polybutadiene and stopping the polymerization with an epoxy compound, a hydroxyl group may be introduced at the end of the car, and [K this seven bales can be obtained.] - Then, a polyolefin having hydroxyl groups at both ends is obtained.Polybutadiene subjected to 0 hydrogenation and 1 is obtained by 1. ! - Clamping, 1.4-) Lance clamping, 1,4-cis bonding, etc. may be included. a little water 5o
It is desired that the ratio of 1.2-condensation is high from SA to 1L.There is no above-mentioned functional group at all other than both ends of the polyolefin, that is, in the middle of the main chain O, and 100-functional groups are introduced at both ends. However, especially during radical polymerization, it is unavoidable that thousands of functional groups are introduced in the middle of the main chain due to chain transfer. It is also difficult to introduce functional groups to both K and 10 terminals when polymerization is terminated. Therefore, as the ninth O polyolefin component for producing the copolymerized polyamide of this li@, one molecule of #IIA contains the above functional groups. It is possible to use a polyolein in which 1 and 2 are introduced, and the number of functional groups in the molecule is 1.
5-2.2 polyolefin is jl! It can be suitably used for.

Also, things that have two or more double bonds! -〇In order to completely hydrogenate the polymer, it is a technical requirement), therefore, as the rounded polyolefin component of the copolymerized boria electrode side structure of this li@, the hydrogenation rate O water with a hydrogenation rate of 70 or more is required. Added polymers are preferably used, and hydrogenated polymers with a hydrogenation rate of 90 or more are more preferably used. Hydrogenated polymers with a hydrogenation rate of less than 100 may not be technically polyolein in the narrow sense due to their structure, but the polyolefin component Kld referred to in superposition@,
Polymers with a hydrogenation rate of less than 100 cells are also refined.

Experiments have shown that the molecular weight of the polyolefin component is 1.
o (If it is less than 1, the water absorbency will decrease by 1 and the effect will be small,
10,000) In the case of very hot weather, it is difficult to obtain good physical properties, so it is desirable that the average molecular weight is between woo to o, o o o. Regarding the copolymerization ratio of Takei Oka, if the polyamide polymer component exceeds 99 parts by weight, 4) the waxy content will be 91 parts by weight, which is the same as the boria-based resin without a fin component, and the polyolefin component will be 91 parts by weight. If the weight part is exceeded, the properties are almost the same as those of polyolein, which is undesirable. The copolymerization ratio is preferably the boriad polymer component vs.
The weight of the polyolefin component is ~7 o.

The copolymerized polyamide resin of the present invention is polymerized by a method essentially similar to the rounding method used to obtain the polyoleain, depending on the polyoleain used. In most cases, the polyester fin component constituting the copolymer is combined with the polyamide molecule component.
The copolymerized boriaodide of the present invention can be obtained by copolymerizing the same polymer as that used in polymerizing the IL polymer.

Finally, in order to adjust the molecular weight of the ζOII copolymer, a diamine or a dicarboxylic acid can be added, taking into consideration the 4 rules of the polyolein component. As the diamine, for example, hexamethylene cyanide, dodecamethylene diamine, etc. Alkylenesia (n, for example, Schiff Cao Heki! Njia Den/, such as Alkylenesia (n),
For example, an aromatic diane such as zeelendiain, ichorondiane, or the like can be used.

As the dicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dodeca/diacid, aliphatic carboxylic acids, and aromatic dicarboxylic acids such as phthalic acid can be used.

On the other hand, when the blind group of the polyoleain used is a hydroxyl group, the copolymerization method for obtaining a superposition-〇 copolymerized boria-dened resin may be either bulk polymerization, l- or -mu-polymerization. In order to adjust the molecular weight of the copolymer, a dicarboxylic acid can be added, taking into account the pattern of the polyolefin component. Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and dodecanoic acid, and aromatic dicarboxylic acids such as aliphatic dilboxylic acid and phthalic acid. To synthesize the copolymer polyamide resin according to this li@ using polyolefin,
By condensation reaction of dicarboxylic acid and amino acid or dicarboxylic acid and cyanide, or by polymerization in the presence of dicarboxylic acid, polyamide oligo!- having a carboxyl group at the terminal is formed, A p-plotter copolymer is formed by an ester formation reaction between the terminal carboxylic acid group of this oligomer and a polyolefin having hydroxyl groups at both ends.The polyolefin diol may be added after the synthesis of the boria-based oligomer, or It is also possible to coexist from the beginning of polyand synthesis so that the reaction for forming an amide bond and the reaction for forming an ester bond occur in parallel. In the formation reaction, the equilibrium of these reversible reactions is rounded, the amide bond formation occurs first, and the plotter copolymer is completed (by the ester bond formation reaction) by removing the desorbed water under reduced pressure at high temperature. @ is required.

Alternatively, a condensation reaction between a polyolefin diol and a dicarboxylic acid is first performed to synthesize a polyester oligomer having a carboxyl iron group at the terminal, and in the presence of this oligomer, a polycondensation reaction between an adenanoic acid or a dicarboxylic acid and a diamine, or A method of conducting M-term polymerization of a lactam to obtain a block copolymer through a monomerization reaction accompanied by a transesterification reaction,
Or the above-mentioned polyester oligomers, boria, and idooligos! A method of producing a block copolymer by a nine-condensation reaction accompanied by a transesterification reaction (by a reaction of -) is also popular.

In the production of the copolymerized polyamide resin of the present invention, a titanium-based catalyst gives good results, so tetrabutyl titanate,
Tetramethyl titanate, 1tetraalkyl titanate, potassium titanium schellaate, and titanium metal salt of autocycate are preferred.Other catalysts include dibutyltin oxide, dibutyltin laurate, autotin compound, and vinegar**. This includes own ship compounds.

In addition, in a small amount of copolymerized IIM, dimethanol and 1,6-hexanediol can be used.

A diol component and a multi-blind agent such as trimesic acid, glycol, and pentaerythritol may be contained.

The copolymerized polyamide resin of the present invention is a block polymer consisting of a polyamide polymer component and a polyolein component, and the molecular weight of the copolymerized polyamide resin of the present invention is about 1.000 as a number average molecular weight.
It is ll.

The copolymerized polyamide resin of the present invention is coated with stabilizers such as oxidation stabilizers, thermal decomposition stabilizers, and light stabilizers during polymerization or after polymerization and before molding, as well as hydrolytic storm reforming agents, colorants, flame retardants, and reinforcing agents. Additives such as materials, fillers, various molding aids, and lubricating agents may be optionally mixed and used.

The copolymerized polyamide of the present invention has a low water absorption rate), has little change in dimensions and physical properties due to water pressure, and has good thermal stability, so it is suitable for use in molded products by rounding, injection, extrusion, etc. This copolymer can also be used as a thermal adhesive with a low water absorption rate, an S* adhesive, and a coating agent. It is flexible) and can be used for various applications as an elastomer requiring rounding and flexibility with excellent impact resistance. Ninth, the impedance temperature II! 4 for use as a heat-sensitive element in electric blankets and electric carpet baskets that utilize dependence and thermal fusing properties.
11 can be advantageously used.

Moreover, the copolymerized polyamide resin of the present invention is made of nylon-11
, 12, 612, and the like. The blending amount is the above-mentioned Bolioid resin 9! ,! 0.01 to 70 parts by weight of the copolymerized polyamide resin of the present invention per 50 parts by weight.

Next, the present invention will be explained in examples.

Example-1 --Adenododecanoic acid ink! , 6f%a, #-dodecane dicarbonate 94.541 was subjected to a condensation reaction under a nitrogen atmosphere in a separable flask with a stirrer, and the number average molecular weight (Mn) was 14. ?Water-volumized polybutadiene with hydroxyl group at the end of ?O 2 ?, 4
t and dibutyltin oxide 0. Add OI f;
Page K 1? React for 7 hours at 0° C. under nitrogen flow. 14 tons of the obtained 90% combined product was transferred to a stainless steel bomb cylinder, and 1■III! 0 under reduced pressure 2
React at 10°C for 1 hour, 2!10°C for 2 hours, and at 270°C for 8 hours. What is the number average molecular weight of the obtained polymer according to end group analysis? , 100 and 1 Poly got 90 by being proud of the strong sheet! - Crushed toluene < Yopyutxley extraction for 1 time and 9 hours - Hydrogenated polybutadiene, which has a hydroxyl group at the end that is soluble in toluene, can only be extracted directly from the plotter. It shows that it is almost completely KIIJζ, and it is 9 points! -Otori-Tarezor i
11. Mar@j was measured at 25°C in a 0.5WtIsO machine and found to be 1.22.

Obtained nine poly! - elemental analysis value is 0784 weight -1n
t z, i weight reference, 1M, - weight 1, that of the eyelid value 077, 1 weight bag, II 12. I weight bag, M ink, 7
The weight is 11sK, and the weight is within the range of 11Al1, and the weight is 9.5mm, and the nylon-11 is suitable for @721S.

15sS, 1!40, 1100 m-14Dll
Characteristic 1k 2942ts for yield and water bulking polybutadiene
-'' absorption and the ester bond KJ that connects the two, 1llllL of 17y6m-1 can be seen.9.

Example-2 m-7ζ nododecanoic acid 41. IP%#-mono-dodeca/dicarboxylic acid 14? and a hydroxyl value of 4 m ([
011If/t), at 100℃ 14
Pole's polyethylene oligomer 14.7- and dibutyltin oquinide O, O it were charged into a maple helical ribbon stirring-attachment 20- autotarepe and heated under a nitrogen stream at a voltage of K1? l) Hold the reaction for 4 hours at ℃.
Raise the temperature with C bottle and IK! After raising the temperature to 270° C. in the dark, the mixture was kept at that temperature for S hours to react. Poly obtained! −
is in m-cresol, o, swt, Il & direct, 2M°C.
When I fixed 1reJ, it was 1.2 ink, which was 9.

Obtained nine poly! The elemental analysis value of - is 0 74.4 wt.
H1! , black weight, 1149 weight, weight layer theory value, respectively 074.1 weight, 1112.4 weight, MS, 0
I'm afraid I'm wrong! ■Take a break inside, then go to 9. The IR spectrum shows 72s, which is characteristic of nylon-11.

1sSs, 1440, 32@O5-10il [and Ho9! f V 7 and the 2?10--1 absorption derived from the methylene chain of nylon-12 and the 1750s-'' absorption NIL of the ester bond connecting the two are observed.

Obtained nine poly! - is coarsely crushed and mixed with toluene p-sock V-
After 10 hours of extraction, only traces of the polyethylene oligomer soluble in toluene could be extracted, indicating that block cocondensation was almost entirely occurring.

Also, D 80 (Diff@r@ntlal loan
The melting point is 177°C, which is 9.

When immersed in water at 40°C for one hour, the water ratio was 0.78. @t % g, s-dodecanedicarboxylic acid 1.6 and two or more hydroxyl groups in one molecule in both ends and in the chain, so the hydroxyl value is 47
(KOH19/t), viscosity at O℃? 30
Poite's polybutene-1 oligomer 16.4f% dibutyltin oquinide was charged into a 100 d autotalepe equipped with a double helical ribbon stirrer.
Under nitrogen flow at normal pressure? (Carry out the linear combination reaction for 1'C for 4 hours, and then reduce the pressure of K O,t mN@O for 1 hour!1
The temperature was raised to 0'C in a bottle, and then the temperature was raised to 270'C over 2 hours, and the reaction was then maintained at that temperature for 2 hours to complete the reaction. The nine polymers obtained were prepared at a concentration of 0.5vt in cresol.
Measure r.l at C and get 1.40f6')9.

The elemental analysis value of the obtained nine polymers was 074.4 weight, [
11.4 weight, M4. ? In terms of weight, the values are 074.2 weight, 1112.4 weight, and 15.0 weight, which are all within the normal range. Nylon-1 for the I-Otori spectrum! 41 molds 1 to 7! I.

11! ! Is * 1440 s violent!・Os-"0 absorption and polybutene-1% characteristic &!?41#-1Lt) absorption and due to the ester bond that connects both 17 S 6
cm-1 was observed, and the nine polymers obtained were coarsely crushed,
Sotutus V-extraction with toluene was performed for 10 hours, but no trace of polybutene-1 oligomer soluble in toluene was found.
Show that j[L is not extracted and the block cocondensation has completely occurred.

The melting point of DIOK was 172°C, which was constant.

After being immersed in water at 40°C for one hour, the water absorption rate was 0.5. s 7 F 4 Hydrogenated polybutadiene with carboxylic acid at both ends (1,! 9614 hydrogenation of polybutadiene with 60 or more vinyl bonds, hydrogenated with terminal carboxylic acid groups lLO, 9
115tn*q/l) H,? Put 2- into an Erlenmeyer flask, and pour it in while pouring 11ml of Erlenmeyer. 12A (condensation begins with the melting of nododecanoic acid), water comes out in the form of bubbles. The mixture was heated at 30° C. for several hours, then cooled, and the polymer was taken out from the Erlenmeyer flask. A light yellow, translucent, impact-resistant polymer was obtained, and the ratio of nylon 12/hydrogenated polybutadiene/hetyl methylene cyano condensate component was as high as 707 BO.

This polymer was made into metacresol K11 ljl, made into 1 S liquid, and jl! ICK1 has 1.4i''e when determining the viscosity versus viscosity.This polymer is press-molded into a flat plate and immersed in 40℃ water for 10 days.If the water absorption rate is fixed using a DuPont water needle, then it is 1.
．． 21 I regret it.

Also, I) IOK is constant and the melting point is 17! ℃ and nine.

Elemental analysis values tIII-IK of this polymer are shown.

Table 1 The infrared absorption spectrum of this polymer includes 740all e2
? There is weak absorption in 40ar1.

Yoshivagina example - 12 aden nododekan Shun 4? , 11 t, Hechuname Terenji Aan 04? v, nona-hydrogenated polybutadiene ij used in Example-4! A transparent, hard, and impact-resistant polymer was obtained after cooling.

This polymer is nylon 1! Iwun/Hydrogenated voluptasie/-
To 1? The ratio of the same ethylene diene condensate component is 90/1
To hide 0KII.

This polymer was summed and determined in the same manner as in Example-4, and the relative value was 1.70% water absorption 1.4! It was melted at a melting point of 176°C.

The elemental analysis values of this polymer are shown in jl-2.

Table 2 - Example 6 64.51 t of 12-annododecanoic acid, 2.41 f of hext methylene cyanide, and 748.20 t of nonahydrogenated polybutadiene used in Example 4 were charged into a boo-separable flask and the electric capacity was increased. Pour the water under the sink and heat at 220℃ for 2 hours while stirring. A pale yellow, #1 almost transparent flexible polymer was obtained. This polymer has a ratio of nylon 12 component/hydrogenated polybutadiene component to methylene cyanide condensate component.
O/I OK@ghost.

This polymer was tested in the same machine as in Example 4, and the results were 9.

The O elemental analysis values of this polymer are shown in Table IK.

Table 5 The infrared absorption spectrum of this polymer includes, in addition to the absorption of the nylon 12 polymer, 76rm *28! Oa
s'', 2?400s'' K weak absorption Example-7 12-inododeca/acid 52.7 at, hex-methylene siaa 5,661% Nona-hydrogenated polybutadiene used in Example-4! 7.48 t was charged into a 50011J size rubble flask, and polymerization was carried out in the same manner as in Example-6.

A pale yellow, extremely flexible polymer was obtained with a round shape.

The polymer is nylon 12 components/hydrogenated polybutadiene.
The ratio of hexamethine/cyaine condensate components is 30/70
to be with you.

As a result of using this polymer at the same 11 KL as in Example 4, the relative volume [1.18% water absorption rate 0. ? i, melting point 15℃'
Met.

Table 4 shows the elemental analysis values of this polymer.

Table 4 The infrared absorption spectrum of this polymer includes, in addition to the absorption of nylon 12 homopolymer, 760s-1, 2140s
%2?40s There is weak absorption of K.

= 1 Example-8 74.40 t of 12-aryan nododecanoic acid, 5.・O#, to life t methylene chloride 1j11
-1 Hydrogenated polybutadiene used in Example-4 24.10
1 was placed in a 500 aJ separate flask and heated at 240° C. for a period of time with stirring under nitrogen flow. A light yellow, translucent polymer was obtained. This polymer had a ratio of nylon 12 components/nylon 6 components/water-volibutadiene-hexylmethylenecyamine condensate component of 707S721sK.

The physical properties of this polymer were kept constant as in Example 4, with a relative viscosity of 1.40 and a water absorption rate of 1.40. s7 overseas, melting point 168
℃ and 90. The elemental analysis values of this polymer are shown in Table 5K.

Table-5 Example-9 11-denoundecanoic acid 74.89 F, +1 methylene diamine 1. S 7 f and 211.92 t t 500 d of the nona-hydrogenated polybutadiene used in Example 4 were charged into a separable flask, and polymerization was carried out in the same manner as in Example 8. A pale yellow, translucent, impact-resistant polymer is obtained.

This polymer has a ratio of nylon 11 component/hydrogenated polybutadiene-hexamethylene cyakine condensate component of 7 o/s
oK411m.

This polymer was stabilized in the same manner as in Example 4, and as a result, the relative viscosity was 1.46, the water absorption rate was 1.41 bags, and the melting point was 186°C.
One ninety.

Table 6 shows the elemental analysis values of this polymer.

The infrared absorption spectra of the polymers shown in Table 1 include absorptions of 760 m-'', 2960 m-'' and 2960 m-'' in addition to the absorption of nylon 11 homopolymer.
−” K @ i absorption kaai.

Similarly, the melting point of nylon 11 film polymer is 192°C], and the water absorption rate is 1.9 cm.

Example-10 40! In the autoclave, in lauryl lactam 14 @,
Nine hydrogenated polyp I diene used in Example-4 578t,
Hekinamethylene diane s1.4F.

After charging 700F of water and purging with nitrogen, the temperature inside the can was raised to 270C over 5 hours.

During this time, the pressure was released and adjusted so that the internal pressure was 2Of#/s. 0 and gradually lower the temperature to 250°C. At the same time as the pressure release was completed, nitrogen was flowed into the autoclave 1 and after 2 hours, the dyed mixture at the bottom of the autoclave was extruded and pelletized.

This polymer has a ratio of nylon 12/hydrogenated polybutadiene-hexamethylene diamine condensate component of 70/black OK
Sugiyuu.

The relative viscosity f of this polymer is 1.1s7.

A nylon 12 homopolymer with a relative viscosity of 1.90 and this copolymer were mixed in a weight ratio of 7 Q/S O, and 50/! 1o
il and L were combined, extruded into a -cm extruder using a 5osaφ extruder, and pelletized to obtain a blended product. A blend of these two types of copolymers and a nylon 12 homopolymer of Sugi Taicho J [1,90] were molded into a Charpy impact test piece with a notch.
The Charpy impact strength at °C and O'cKjIk was kept constant. The results are shown in Table A.

It can be seen from Table 7 that this copolymer has an excellent impact resistance of 11 kK, and that blending this copolymer improves the impact strength of the nylon 12 film polymer.

Reference Example-1 Example-1 An oritljji sheet is held in 40°C water for a period of time, and the water content after the rounding can be 0.802 weight.

The impedance of this sheet was measured in the dry state after vacuum drying at 70°C and in the state 1 after being held in water at 40°C. 'ρ-and 4x10'#sf”
Well, the difference is only 0)
°C, heat of fusion 7. I QILj / f's clear ponga nature ^
A friend that shows the melting behavior of molecules. In this way, the impedance is 1
Since it can be used for heating and use due to its clear melting point, it
Dodenoma can be suitably used as a heat-sensitive element for electric blankets and electric carpets.

Reference example-1 4 sheets of nylon 12 with a number average molecular weight of 24,000
The impedance of this sheet was 70°C when it was kept in water at 0°C for a period of time and the water content after the round was 1.6%.
X Measured after drying in the air and after holding in water at 40°C.
Qexs and 1. I X 10'ρ-, and the difference is 1. ? Also send it to X 10 g-.

Even on this sheet, D80 was measured and the melting range was 164-14℃, the peak temperature was 178℃, and the heat of fusion was 9
．． 20&j/t″e#).

12 )L bar

Claims (1)

[Claims] 1. Since it has one or more repeating units represented by the following general formula (1) or (2), the polyamide polymer component has 99 to S weight parts and both terminals are carboxylic acid groups or amino groups. or a new copolymerized polyamide resin obtained by copolymerizing 1 to 91 parts by weight of a polyolefin component having an average molecular weight SOW of 10.000, which is a hydroxyl group) n00- (1) (in the formula, nFis is an integer of 11) -mtxmiaoyoo -(2) (wherein, X is Ol, H, (m is 4 to 110111k)
. Represents an isophoro7 group, a phenylene group, or a Schiff-silene group, and! (represents Oj town j (j is 4 to 104D regular), Hue ink group or V/Lohe middle silene group) 2 Is the ratio of the polyamide bird molecular component and polyolein component to the boria-based polymer component? Polyolefin ingredient for 5-10 weight cranes! S ~ 70 parts by weight @- of the patent claim
A copolymerized polyamide resin with a special reputation.