JPS59102922A - Novel polyester resin - Google Patents

Abstract

PURPOSE:The titled resin having improved antistatic properties, durability, water absorption properties, adsorption properties, having a copolymerized amino group in a structural unit, obtained by copolymerizing a polybasic carboxylic acid and a polyhydric alcohol with a specific polyhydric alcohol containig an amino group. CONSTITUTION:(A) A polybasic carboxylic acid (e.g., isophthalic acid, etc.) and a polyhydric alcohol (e.g., ethylene glycol, etc.) or another compound to be esterified is copolymerized usually at 150-300 deg.C with (B) a polyhydric alcohol (e.g., trishydroxymethylaminomethane, etc.) containing an amino group having heat stability at <=300 deg.C, to give the desired resin. The amount of the component C used is preferably 0.1-30wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyester resin in which amide 7 groups are copolymerized in the constituent units of the polymer.

Polyester fibers are originally hydrophobic fibers and have poor water absorption compared to natural fibers as well as other synthetic fibers, and inevitably generate static electricity. In addition, since polyester resin exhibits excellent adhesiveness to polyester fibers and textile products, in recent years, fiber processing agents, adhesives, coating agents, etc. containing polyester resin as a main component have been developed. However, market demands have been improving year by year, and these products have become extremely anti-static, durable,
Performance such as water absorption/adsorption properties and prevention of loss of fastness to friction are required, and research has been conducted into the introduction of cationic groups into resins.

However, copolymerization of cationic groups such as amines is extremely difficult due to their thermal instability, and no examples have been put into practical use.

The present invention solves the above problems and provides a new polyester resin that can be widely used as a fiber processing agent for polyester fibers and blended fiber products, a binding agent for glass fibers, and other applications. This new polyester resin is
It is characterized by copolymerizing a polyhydric carboxylic acid, a polyhydric alcohol, or another compound capable of a polyesterification reaction with a polyhydric alcohol having amide 7 groups that has excellent thermal stability at temperatures below 300°C.

In the present invention, polyhydric carboxylic acids include aromatic polybasic acids in general such as isophthalic acid, terephthalic acid, and trimellitic acid;
Aliphatic polysalts such as adipic acid and sebacic acid M acids in general, l
, 2-cyclobutanedicarboxylic acid, 2,6-dicarboxypyridine, and other polybasic acids with alicyclic or heterocyclic rings;
Furthermore, it includes all acid anhydrides thereof, regardless of whether they are saturated or unsaturated.

In addition, the polyhydric alcohol in the present invention includes aliphatic, aromatic, or alicyclic polyhydric alcohols in general, and examples thereof include ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, trimethylolpropane, Examples include pentaerythritol, sorbitol, bisphenol, etc., and also oligomers and polymers of polyhydric alcohols such as polyethylene glycol and polypropylene glycol.

Next, the most important component in the present invention, 300'C
In the following, examples of the polyhydric alcohol having an amine group with excellent thermal stability include 2-amino-2-methyl-1
, 3-propanediol (hereinafter abbreviated as AMPD),
2-amino-2-ethyl-1,3-propanediol (
(hereinafter abbreviated as AEPD), trishydroxymethylaminemethane (hereinafter abbreviated as Tris HM AM), etc., and the present invention also includes the use of two or more of these in combination or modified without neutralization. . Here, 30
Excellent thermal stability below 0°C means 300'C
This means that there is no effect of extremely inhibiting polymerization within the following temperature range, and even if coloration occurs, the reaction will proceed and a polymer copolymer will be obtained as a result.

It is preferable to add 0.1 to 30% by weight of the total amount of other components to this polyhydric alcohol having an amine group with good thermal stability; if this exceeds 30% by weight, thermal decomposition may occur during polymerization. On the other hand, if this amount is less than 0.1% by weight, the required performance such as antistatic property, durability, water absorption/adsorption property, and prevention of loss of fastness to friction will be deteriorated. It becomes insufficient. The timing of copolymerization of this component may be at the time of initial preparation, or for example, in a two-step reaction method leading to transesterification and polymerization, it may be added at the time of polymerization after completion of transesterification. There is no problem even if they are added during the reaction. In addition, copolymerization is possible within the reaction temperature range of ordinary polyester-based polymers, that is, 150 to 300°C, but in order to prevent reaction inhibition due to thermal decomposition, the reaction temperature must be 250°C.
At C or higher, it is preferable not to react for 1 hour or more.

Next, the present invention will be explained in more detail with reference to Examples.

Note that parts and % in the examples mean parts by weight and % by weight, respectively.

〔Example]〕

Dimethyl terephthalic acid 194m (1 mol), triethylene glycol 22.5 parts (1.5 mol), molecular weight 15
After initially charging 2 parts (0.2%) of AMFD in 500 parts of 4o polyethylene glycol, transesterification was carried out at 230'C for 3 hours in an inert gas stream, and then 3 mm.
Polymerization was carried out at 250'C under a reduced pressure of Hg for 1 hour to obtain a white wax-like fiber processing resin. This was dispersed in hot water and diluted to an aqueous solution with a solid content of 1%. processed by law. It is 180'CX
Samples were heat-treated for 30 seconds and compared with those treated with a resin containing no AMP D in terms of water absorption, antistatic properties, and SR properties. The results are shown in Table-1.

Table-] (]) Sample description J161 Blank, water treatment only/IG, 2 Conventional resin treatment without A M P D, coating amount 0.5% 7763 Resin treatment according to the present invention, adhesion 0. 5% (
2) fk: Washing method Using a household washing machine, wash Zabu Enzyme (weak anion activator manufactured by Kao Soap)], Vl, 40°C for 0 minutes,
Wash with water for 5 minutes, spin dry, and consider this cycle to be one wash.

(3) Cut the water-absorbing cloth into 2mm x zoommm pieces and store them at room temperature.
The end 20m71r is immersed in distilled water, and the height of the water rising in 3 minutes is measured.

(4) Antistatic properties Kyoto University Kaken 2 Rotary Static Tester (Rota)
ry 5tatic Te5ter), Tetron taffeta was used as the friction cloth, 20°C, 140% RH.
Rotation at 400 rpm was applied at the bottom, and the charged voltage was measured after 1 minute had elapsed.

(5) S R pollution bath composition Carbon black 0.59 Hardened beef tallow oil 0.59 Liquid paraffin
Contamination treatment was carried out in a 1.5g contamination bath with 15 steel balls of 160πt1 at 80°C for 60 minutes using a round-o-meter. Cleaning with Zabu Enzyme 1 f//300
ft for 15 minutes at 80°C, washed with water, and then dried.

Determined by gray scale for contamination [Example 2] Using the same resin dispersion used in Example], polyvinyl amundsen-dyed fabric was treated in the same manner as in Example 1, and the friction fastness during treatment and after washing five times was evaluated. Table 2 shows the effects on dry and wet conditions.

Table-2 Test method JIS-0489 A Gakushin type friction fastness tester is used.

Wiping cloth (dye) Resolin Blue BB 8% 0. lol
, f.

[Example 3] 155 parts (O, S mol) of dimethyl terephthalic acid, 33 parts (0.2 mol) of isophthalic acid, 114 parts (1.5 mol) of propylene glycol, and 420 parts of polyethylene glycol with a molecular fjt of 6000 were mixed with an inert cassette. in airflow, 230
After transesterifying with 'Q for 3 hours, AEE'D was transesterified with 20
Added 0 parts (28%) and heated at 250°C under reduced pressure of 3 Hg.
Polymerization was carried out for 30 minutes to obtain a pale yellow wax-like resin for fiber processing. This was dispersed in hot water and treated on a polynis plutoskin white cloth in the same manner as in Example 1, and the antistatic property was compared with that when treated with a resin containing no AEPD. The results are shown in Table-3.

Table 3 Same as Test Method Example 1, how many clothes are 0.5% From this result, when treated with the resin according to the present invention, 20%
It can be seen that it exhibits antistatic properties even after multiple washings.

[Example 4] Terephthalic acid lz: 5ffts (o, s mol), adipic acid 29 parts (0.2 mol), ethylene glycol 62 parts (1 mol), 1,4-butanediol 90 parts (1 mol)
, A to 500 parts of polyethylene glycol of molecule M400
After initial charge of 1 part (0.1%) of MFD and transesterification at 230 °C for 3 hours in an inert gas stream, 3 #
Polymerization was carried out at 2508 C for 60 minutes under a reduced pressure of 1 Hg to obtain a white wax-like fiber processing resin. This was dispersed in hot water and treated on a polyester Amundsen dyed fabric in the same manner as in Example 1, and Table 4 shows the effect on the abrasion fastness when treated with a resin that does not contain AMPD.

Table 4 Same as test method Example 2, 0.5% test cloth dye) Dianix Navy Blue 2R-F3E
8% o, w, f.

From the following results, it can be seen that adding 0.1% AMFD significantly improves the effect on the friction fastness.

[Example 5] 155 parts (O, S mol) of dimethyl terephthalic acid, totican-2-1'f? 52R (S (0.2 mol)), 124 parts (2.0 mol) of ethylene glycol, 300 parts of polyethylene glycol with a molecular weight of 6000, and 30 parts of polyamide obtained by interfacial condensation polymerization of hyperazine and adipic acid chloride were mixed with an inert gas. Suqi 15iLl: 43.230
After transesterification for 3 hours under reduced pressure at 'C, AKPD
Add 100 parts (15%) of
CX was polymerized for 40 minutes to obtain pale yellow varnish-like fiber 1+JO resin. Table 5 shows the absorption RK test results when a polyester toskin white cloth was treated in the same manner as in Example 1, and the AEPD was treated with a non-self-setting resin.

As in Test Method Example 1, adhesion amount was 0.5%. This result shows that when AEPD is blended, sufficient water absorption performance remains even after 20 washes.

[Example 6] Dimethyl terephthal m 97ffl ((0.5 mol),
63 parts (0.3 mol) of trimellitic acid, 93 parts (1.5 mol) of ethylene glycol, 26 ff of dodecane-2-acid
ls (o, 1 mol), 5 parts of trimethylolpropane (
0,04 mol), 5-sulfoisophthalic acid 3OW (0,
1 mol) was transesterified at 250'C in an inert gas stream for 5 hours, then 10 parts (3,2
%) and polymerized at 250° C. for 1 hour under reduced pressure of 3 mm Hg to obtain a hard finishing fiber processing resin in the form of a pale yellow translucent resin. Table 6 shows the results of dissolving this in hot water and treating the polyester tack in the same manner as in Example 1, comparing the hardness of the texture with that when treated with a resin that does not contain Tris HM A Iφ. show.

Table-6 (y/1omm) Test method JIS L 1096 E method (texture meter)
Measure with. The higher the number, the harder the texture. heart 1
Coating amount: 0.5% [Example 7] Using the resin of Example 6, a T10 mixture (Tetron 35
Table 7 shows the results of hardness measurements when treated on cloth (65% broad).

Table 7 (g/lomm) Test method From the results of Example 6 and Example 7, which are the same as Example 6, it can be seen that the texture is durable when treated with the resin of the present invention containing Tris-HMAM. .

[Example 8J 74 parts (0.5 mol) of phthalic anhydride, 4 parts of maleic anhydride
831 ((0,5 mol), propylene glycol 152
(2,0 mol), 20 parts of polyethylene glycol with molecules @ 4000, and 1 part of hydroquinone were reacted at 150 °C for 1 hour in an inert gas stream, and then AEPD]0
(3.4%) was further polymerized at 200° C. for 7 hours at normal pressure to obtain a resin for glass fiber convergence side having an acid value of 60.

Next, water was gradually added to this resin liquid while stirring at high speed to prepare a self-emulsifying emulsion with a solid content of 40%. and,
Using this emulsion, a sizing agent having the following composition was prepared.

Composition of sizing agent Polyester emulsion above 7.0% acetic acid
0.1% water
92.5% This convergence agent was applied with a roll coater to a 10μ, 200 filament glass fiber that was being converted into fibers, and after convergence, it was wound up as a strand on a coronod, and the weight was 1.5%.
kg of cake. This cake was heat treated at 130°C for 10 hours, and then roving was made by arranging 60 cakes on a platform.

This was cut with a cutter to create a 25-meter long chopstick strand, but no static electricity was generated and no damage to the cutter was observed. The amount of charge on the deposited part of the chopped strand is -0.3 KV (20'C).

60% RH). In a roving made using an emulsion containing no AEPD with the above-mentioned sizing agent, static electricity generation was significant and the amount of charge was -7, OKV.

Next, the glass content is 50% using chopped strands,
An FRP laminate with a thickness of 1.5 mrrr was made, and in order to judge the adhesion between the glass fiber and the resin, it was boiled for 5 hours and the transparency retention rate was examined. It was improved compared to the case of using an emulsion without blending. The results are shown in Table-8.

Table 8 [Example 9] 44 parts (0.3 mol) of phthalic anhydride, 3 parts of isophthalic acid
3 parts (0.2 mol), 48 parts (0.5 mol) of maleic anhydride, 93 parts (1.5 mol) of ethylene glycol, 20 parts of polyethylene glycol with a molecule of ff12ooO, and 1 part of hydroquinone in an inert gas stream. After reacting at 150°C for 1 hour, 4 parts of AMPD and 20 parts of AILPD (combined 111%) were added, and the mixture was further polymerized at 200°C for 7 hours at normal pressure to obtain a resin for glass fibers with an acid value of 58. This was made into an emulsion in the same manner as in Example 8, and a sizing agent was prepared in the same manner using the emulsion and applied to a woven glass fiber to form a roving. The amount of static electricity generated when this roving is cut with a cutter and the amount of static electricity generated after boiling the laminate (5
Example 8 and Example 9 show that the resin of the present invention can be used in the field of glass fibers and sizing agents. It is also useful to reduce static electricity when cutting roving with a cutter, reducing dust and F.
It can be seen that this has the effect of improving boiling resistance during RP molding.

that's all Agent Patent Attorney Atsushi Yasufuji

Claims (1)

[Claims] (1) Polyhydric carboxylic acid, polyhydric alcohol, or other compound capable of polyesterification reaction, and
A novel polyester resin characterized by copolymerizing a polyhydric alcohol having an amine group with excellent thermal stability in C or less. (2> Polyhydric alcohols with amine groups that are thermally stable below 300°C are 2-amino-2-methyl-
]-]+3-propanediol 2-Amino-2-ethyl-1,3-propanediol, or trishydroxymethylaminomethane, the novel IJ ester resin according to claim 1.