JPS596220A - New polyamide copolymer - Google Patents

Abstract

PURPOSE:The titled copolymer useful in hot melt adhesives having good bonding strength even at a low bonding press temperature, consisting essentially of a nylon component having piperidyl rings in the main chain and at least 8 carbon atoms in the methylene chain. CONSTITUTION:The titled copolymer obtained by polymerizing 5-80% nylon salt or equimolar mixture comprising a saturated aliphatic dicarboxylic acid of formula I (wherein A is a bivalent hydrocarbon group derived by replacing part of the H's of a methylene chain of formula II or III with 1-4C alkyls, l is 4- 20, and m is 1-10) and a secondary diamine of formula IV, 95-20% of nylon salt or equimolar mixture comprising an 8C or higher methylene chain lactam or corresponding omega-aminocarboxylic acid and/or an aliphatic diamine and an aliphatic dicarboxylic acid, wherein at least one of the components has an 8C or higher methylene chain, and 0-40% nylon salt or equimolar mixture comprising a 7C or lower methylene chain lactam or corresponding omega-aminocarboxylic acid and/or an aliphatic diamine and an aliphatic dicarboxylic acid, wherein at least one of the components has a 7C or lower methylene chain.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyamide copolymer, more specifically, i) a diamine dicarboxylic acid salt having bispiperidylalkane as a diamine component or an equimolar mixture thereof; The following lactam or its (0-aminocarboxylic acid) and/or consists of an aliphatic diamine and an aliphatic dicarboxylic acid, and at least one component of the diamine or dicarboxylic acid has 8 or more carbon atoms in the methylene chain. The present invention relates to a high-grade polyamide copolymer having a piperidyl ring in the main chain as an essential component such as a certain nylon salt or snow mole mixture. In particular, resins for hot melt adhesives such as fiber-based adhesives include polyethylene, polyvinyl chloride resin, ethylene-vinegar; strong vinyl copolymer resin, polyester, and various other resins. Among these polyamides, polyamide resins have been widely used as permanent adhesive interlinings due to their strong adhesion properties and good dry cleaning resistance. As the tendency for outer materials to become thinner has increased, hot melt adhesives for this purpose are required to be low l crystal melt type and also have flexibility in terms of texture.

As a method to meet this demand, various plasticizers, such as Eva,
Appropriate additions of pensene sulfone butylamide, 2-ethylhexyl p-hydroquine benzoate, 0- and p-)luenesulfone ethylamide, etc. can lower the softening strength and also improve flexibility. However, when applying the method using these plasticizers to the current processing process of interlining 1q and crushing method 1, Hot-melt adhesives applied to adhesive interlinings are generally powder-like, so they are susceptible to soil 14-1. Record i: iJ' 91Q! If you add something that is liquid at room temperature to the inside of the shavings, the hot melt resin powder will flow as a powder! (1) Since it impairs the properties of hot melt resin, it must be blended into the hot melt resin itself in a molten form and then ground into powder, which poses an economical problem. Powdered plasticizers can be added directly to hot melt resin powder and blended, but mechanical vibrations during the process of transferring the plasticizer to the interlining using a machine tend to cause the resin and plasticizer to gradually separate. ,
3 In order to avoid these drawbacks, which can lead to variations in quality, a method is also used in which water is used as a medium, hot melt l-ml resin and plasticizer are dispersed in the medium, and the paste is made into a paste and transferred to the paper or substrate. However, in order to obtain a stable base, it is necessary to add protective colloids and surfactants, and to improve stability and workability, it is necessary to add thickeners and antifoaming agents. These many additives have a more or less negative effect on adhesive strength, and tend to be a factor in deterioration of strength over time.

In addition, the hot melt adhesive Hakukyu containing plasticizer has been used for many years as a bonding material and interlining material (Ia). There is an essential drawback that the texture is lost.

The present inventors, based on the idea that it is necessary to modify the resin itself in order to eliminate these drawbacks, have made extensive efforts to develop a methylene chain carbon having a piperidyl ring in the main chain. They have discovered a new polyamide copolymer containing a nylon component having 8 or more atoms as an essential component. That is, the present invention provides a nylon salt consisting of (1+) (OOC-A-COI (which can be expressed as a saturated aliphatic dicarboxylic acid) or an equimolar mixture thereof). 5 no, [Ishi 80 weight is the person in charge (however, A is -(CI■2)U or -(C H
2) z- is a divalent hydrocarbon group in which a portion of hydrogen in the methylene chain is substituted with an arbitrary alkyl group having 1 to 4 carbon atoms, e is an integer of iE to 20, and 71ba1 to t O's "1" number) (2) A lactam in which the number of carbon atoms in the methylene chain is 8 or more -1, -, or
Nylon salt or equimolar mixture consisting of ω-aminocarboxylic acid: 16 and/or aliphatic diamine and aliphatic dicarboxylic acid, in which at least one component of the diamine or dicarboxylic acid has a methylene chain carbon atom r number of 8 or more +
(3) Lactams having 7 or more carbon atoms in the methylene chain, or their ω-aminocarboxylic acids and /sho/-+
lt, II 11 horns Il'+, diamine and moon power, father ncarpon II ambiguous L'.

It consists of 10 diamines with 1 dicarboxylic acid
The most important component is a methylene chain containing 7 or more carbon atoms. 1', Noshiro Y 斤j Look at it
・The one who prays for the common Chinese and Japanese books.

, - (ni ItOQC-A -COOII (two expressions)) 111 fat father jikarn 1 suggestion is part 1)' white G core / pin il I shi 2, pimeli / r1 anchor, Corri 11th woman, No'hi line convex! 2 /, I- and ゛Meboure 7 no East;, l'(2++)p Q th;
i'&'-.

No'jihi 71.1 yen, Hiba 7 no! 1y,, Tobukanojinonono and I', ! ll'f +'white (E 0 interest. Metyleno 1 East 4 Portrait 2], Su, 1 ()) Higher dicarboxylic acids are 11 esthetically pure, and the c form is human hand <:
+ 1-' or rQf1, and its use is not advantageous.

<1. i'' water (<i, +, charcoal age number 1 or ・
Even if it is substituted with a relatively short-chain alkyl group in 1, it does not significantly affect the polymerizability (it can be used).

This is an equimolar mixture of dicarboxylic acid and bispiperidyl alkane of nylon 1/40 or 5/4 (, (
・Shi 8 () ton - composition ・ 1 ・ ] j, 1711 - (use 1) ne) or this 1 s, if there are less, the piperidyl concentration 1 in the 10 buttons will be lower. -4-hepiperidyl ring, (
(Based on this, the direction 1 of l, 50 + I17. + articulation 11"1 is 1 μm +'> :ll -4\ ・L muko 1 Yoshiki fi detective 11th, ■-li d・'4
gi a) Tozuri l', +Jl a) Copolymer inner surface 1ζ! 1 (Water (< 1 decrease is L゛)rei) ())
1. f+1. -Not.

Next, the carbon atom of methylene-1 denitrate is lactano-ma/ko (0-amino sonorpho
If we take
, ω-unte/lulactam, ω-todecyllactano-tongue and its corresponding a) ω-aminocarboxylic acid kaage I? )Rei).

In addition, at least one component of the diamine or dicarboxylic acid is methylene i'Igf (consisting of an aliphatic diamine having 8 to 1 carbon atoms and an aliphatic dicarboxylic acid) nylon salt, or an equimolar mixture thereof. What about nylon 6)
0, Nylon I (1,1 (1, Nylon salts such as nylon 612, nylon 1212, etc.). Wide fit section,
Please use the word ``a'' in my circle. This methylene chain carbon-
A nylon component containing a component of Nihara-rn or 8 or more and 1)
(14
1+: N similar to 1- with Mui +, 1: ') blended with JL i). The ratio of these two components is tangent/'y'1'4'1 and 1t to water (1...lance or r)? ) Shishiri, Metileno Renkugi 1 carbon D; tr'l; 9. The ratio of the J-V nylon component containing components of h・8 or more is high <F' Roto 1 antithermal water ('L L1 is better, and the LN nylon component containing piperidyl rings is not high) and adhesion ('l has been improved (SaA1i)
FG main methylene chain θ) carbon 1 t1'x (ga 7, l゛J, l
The nylon component C, which contains the components of ・11a), is
1) Physically, it is a monomer or equimolar mixture of ω-caglolacta l or nylon 66), and a) polyamide conjugated l? Affects the iqt point. 1-Nawashi 2. If you increase the composition ratio of this component and add 1° of random 1'1 of the polyamide copolymer, the part where the melting point is low will be reduced.)
ft Z,).

The method for producing the polyamide copolymer is a known method used for producing 1+'4 polyamide.

Industrially, it is advantageous to use the reflux method using water as an initiator.
7:
,).

-1', that is, hispiperidylalkane and fr'z, t
a Nylon consisting of aliphatic dicarbonate 1119 or 1゛)
f1+'t: t or mountain 2. The number of carbon atoms in the methylene chain is 8 or more as a heartbeat component in the predetermined 1.4 of the sound object.
The lactam is composed of [゛)] (m-)'minocarboxylic acid and O.・rta(
1 dicarbont? Nylon I'7171+ having 8 or more carbon atoms with at least one residue of Medileno series 1j
The prescribed use of the proboscis to 11 mols of tobacco is necessary, and in history the number of carbon atoms in the methylene chain is 7.
Add the following polyamide forming ingredients. Add water as an initiator to IL a).

If monoacid is to be added as a polymerization accelerator, it can be dissolved in water and added. The system 1- below is expressed as 471. ? , 4
・、Heating to around 25(+"C) and heating to 11JI for the first time.
Condensation product (~, f-4 produced by reaction under atmospheric pressure 1a) Water is 11' in a nitrogen stream! If heating and infusion is proceeded while releasing, the desired polyamide]・J11 core will be formed.1)11.

4 "No, J11 middle body - (Has, 3 jc and 4 jyo common middle combination fl + formation/X: J, 14 children" I, Kotomokii).

, -1, 1! In addition, the polyamide co-neutral polymer has excellent adhesion to hispiperidyl alkane. .17, Steel, aluminum, etc.
-+, (((ζ illusion, adhesion (1 is also used as a cut, i., 'l'iii; dei,.

J, l, weight, implementation ii'yl- (=mo-), 'iir, bright.

Example-4" l-denononodicarboxylic acid ll-00C (C
l-12) + n -276 of COO11! I
W O) 7 Lasconite j), f nogrovir algol! Add l Ll F, 1, q, 658-7
(11 power to 7, j) 5 knead 1] and served 'no self M. This Jt1 hot bath t+'v- 1:3-G(4
-piperidyl)propano+; :((I finished W4 IQ on 1,9/this 7M n branch!I added 1 of i'M to i'U4' sea lion.L' at the same time as adding more and more) , It is a salt of a dicarboxylic acid and an amine (hereinafter referred to as 1) )) 1= and abbreviated as F)) becomes a crystalline state and precipitates. After cooling, leave the chamber with crystals overnight. Method) Sooty white a1, crystals with cold inopropyl alcohol to obtain I) Pl,1-, about 5: (fl, zo/, two.

In this way I#l2I) P J'vH 4 Fl
(+ , γ [Nryllactam monomer - - +
n (1 3 -F.; 1: Hinonozo "I Lactano, Monomer - I Il 11 9 Stainless Steel
ii. '． ! ,'(Q'rto') Place in a crepe, add 877 g of pure water as an r'f-initiator, and add 10.1 g of omega-aminododecane as an undercarriage accelerator.
Fluorescent f'l Ubitenox M. I) (Jibakaigi-Jl
i. il17) (1. After adding 5 g of nitrogen, completely exchange the system with 1 t'"" of nitrogen, and then add 1 t' of nitrogen to 4 kg/l of nitrogen. ,i,
After changing it to G. P? Edited. In about 3 hours, ′、Jōdō 26
0℃, internal pressure 1', (7)
)is. It took me 4 hours, 1 pause, and 5 hours for this situation (
The crystal IW of the system was heated to 200 C.

At the same time, the pressure was gradually released until it reached atmospheric pressure. This was followed by heating and stirring at 200°C for 5 hours while adding nitrogen at a flow rate of +507/rmn. 1□Zhong Shu (
Lost Strand 1, /I/ 4; IIH Tet hurriedly) Pele, Tizer Te Pellet 1□iT 1. l2,
('.j l) JL /-Polymer-o. 5, q
,,/I (l [I Tn("!r".

H knee) + 7 kukresol lewd ζ 7 r da's 25' (゛nioshi 1 i) opposite 1 dry 1': +-f, l'. I,
i ′I, small “scanning: l; measurement (+) S C
＞に、１、る（、411! I'l'rBi't!1
1::;-(1, (1 5 ”(-te7age) /”
.

Next (, r, use this Bere Toibi liquid fortification powder to make cold rice (1 - add liquid nitrogen /: t-h' c, bottle-type crusher 1 - r B) 6 rice, 'fFli 't)
, Iir , 1,') fi:3 Miku'' /, Hasuno l) (4'I Kei・II II /-.

Next 1(,,,2;j; Nodmelt r+ ,,-1・(11 8 tl) lυ(-Powder Tonodoni 1゛i-Inda/1,?1/2,-
4), 2 Ii [1 ” ('. to] Jll;
PL (3 days - Jl I) - 1111 cotton broadcloth (Il 8++) f heat 1, , Ii
(1'((]) lj, 19%i D-ru(+7
Boi 7 L / 2 5 mm X l 7 Boi / l
・/ 2 5 +III'l; (1 8fl Ii
Im Qi×+1. :3 rrrrtr I () The material was transferred, and the transferred Al/nidon-like powder was applied to the base fabric 1- by infrared rays. tCC60ko(1) , l, Kino's roll' , :4
The material f;H is 5 1#l/ml11, and the transfer to the base fabric is 39/m'.

This adhesive cotton broad was used as test sample 411 to press the cloth with a cotton cloth (IL80). l SeC and the press temperature was kept constant at 1 1
+1 □C to 150 "C" 1 and press adhesive, 2 3 (', 5 () section R Il. I. at 2.11
dyl rh+ for 111'! r&T <ii N;+
b D1. 1) Contact! 6 Thji degrees ill+
Fixed position.

The tensile speed was 20 (l mm/man-Q,
ti)i). IQ l' + Jl ta 1t4 is shown in song storage A in Figure 1.

Compared to 11 bites! Komeni Lauryllactam 40 Naka:,: Section,
Tunoprolactam 3 () doublet, hexyl methylenediamine and todecanodicarboxylic acid: 3 + lΦ: 1; ! ) Leaked polyamide l-', -Jl giant 1'1 coalescence (0.!'i jl / l Fl tl, n
o 4゛,°
°C tGgei) Japanese, 1 I-san II 5-1, 45; I)
SC melting temperature + + o ”C) of 6,3
Micron pass powder is used, 1- and 1-times-conditions are used for cotton profiling.
- M (II 80) K
+i! /, transcription (translation 'su'H,H) l
! l + , zo / n ( ) after cotton bra rJ
-Press with M (II8o) J)j Ii-Trial!
Adhesive strength was measured for Sample 1. This result is the first
The curve C in the figure is shown.

Furthermore, for comparison, lauryllactam'11:% in 0,
Nonophorolacta 1, 25 weight: Juice, salt of hexamethylene diamine and acelaic acid 25 weight>-(%, salt of isophorone diamine and dodeca/dicarboxylic acid 20 weight) (:%
a) polyamide quaternary covalent polymer (relative rod II'r-
1,35; I) SC simple squirrel iM I 7
Using 6゛3 micron pass powder of 5''C), transfer to the same base fabric under the same conditions (transfer: Tsuji 2f1. (i, zo/++I), press adhesion trial with cotton broadcloth (II 80) The results of the adhesive strength measured in the same manner for trial testing are shown by curve I3 in FIG.

From these results, it is clear that bipiperidyl-
Polyamide copolymer containing alkane salt as a component (curve A
) is low 1. 'Ql! Adhesive press relatively low in terms of points? Good blackness 1. Show the strength of the f contact f(・ro).

According to the composition shown in Example Table 1, the tail was No. 1200.7 (
11. As in Example 1, pure water,
Add a small amount of ω-aminododecanoic acid depending on the amount of Φ
The meeting was held. The relative viscosity of the obtained polymer and I
) SC melting peak temperatures are shown in Table 1.

On the other hand, for comparison, lauryllacta l1, cabrolacta l, ↑, 9. which do not have DP salt as a component. Lbi hexamethishi/
Consisting of diamine diamine branch J'3K: ()1-coΦ
Polyamides were similarly neutralized, and comparative examples are shown in Table 1.

Each polymer was made into a powder by cold grinding using liquid nitrogen, and sieved to a 4n powder with a 1-3 micron pass.

Using these powders, in Example 1, cotton 7' was
Load (Powder tonoto coding was performed on 1I8(1)-1. Transfer/i- is 180~IC in both cases)
It became between Of9/711'.

Using this adhesive cotton broadcloth,
) and press adhesion (・, the adhesion was measured. The results are shown in Table IK along with the comparative example. Compared to the comparative example, it shows good adhesion, especially in the region of low press temperature.

Figure 4 +m ノ@,'1'l Explanation Figure 1 shows the cotton broadcloth (rt8o) when the press 11 information IC- is changed.
The adhesion strength I is shown.

Daicel Chemical Industries, Ltd.

Claims (1)

[Scope of Claims] A nylon salt consisting of a saturated aliphatic dicarboxylic acid which can be represented by (11HOOC-A-C(,)OH) or a secondary diamine which can be represented by OH or an equimolar mixture thereof. (However, A is +CH2) e- or -(-CH2) is a divalent compound in which a part of the hydrogen in the methylene chain is substituted with an arbitrary alkyl group having 11 to 4 carbon atoms. Hydrocarbon group, e is a positive integer 1 of 4 to 20, f71 is 1 to 1
(a positive integer of 0) (2) A lactam having a methylene chain of 8 or more carbon atoms or its ω-aminocarboxylic acid and/or consisting of an aliphatic diamine and an aliphatic dicarbonate of 1 yen; Nylon salt or equimolar mixture in which at least one component has a methylene chain of 8 or more carbon atoms, weight ratio 95 to 20 (3) Lactam or its ω-aminocarboxylic acid and/or an equimolar mixture of 7 or more carbon atoms in a methylene chain; or an aliphatic diamine and an aliphatic dicarboxylic acid, in which at least one component of the diamine or dicarboxylic acid has methylene chain carbon atoms of 7 or less, or an equimolar mixture of at least one type of nylon salt or an equimolar mixture of O to 4() A new polyamide copolymer obtained by polymerizing from Φ and Φ.