JP2002212297A - Polyester-based reaction mixture composition and the use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide aqueous dispersion imparting excellent characteristics such as surface smoothness, a hand feeling, hydrophilicity, and antistaticity to fibers, paper, films, plastic molded products and the like. SOLUTION: A polyester-based reaction mixture composition containing (1) and (2) below is converted into an aqueous dispersion and is served as a treating liquid, (1) a transesterification product obtained by reacting an ester (A) obtained from an 8-20C fatty acid and a polyalkylene glycol with an aromatic or aliphatic polyester or a block copolymer of the polyester with a polyether, (2) a reaction product obtained by reacting three compounds B, C and D with the polyester above, (B) a polyalkylene glycol-modified silicone resin (optionally bearing an amino group, an epoxy group or a carboxyl group), (C) an ether obtained from an 8-20C higher alcohol and a polyalkylene glycol, (D) a polyalkylene glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to fibers, papers, leathers, films, plastic moldings, cosmetic base materials, etc., which have good smoothness, good touch, hydrophilicity, antifouling properties, antistatic properties, etc. The present invention relates to a polyester reaction mixture composition capable of imparting the following characteristics, an aqueous dispersion thereof, and uses.

[0002]

2. Description of the Related Art A block copolymer obtained by reacting an aromatic polyester with a polyalkylene ether glycol is:
For example, it is described in JP-B-49-16774. These block copolymers are hydrophilic, antistatic properties, useful as a polyester with excellent antifouling properties,
These block copolymers have rubber elasticity and are widely used in this field.

[0003]

However, it is difficult to disperse these block copolymers in water to form an aqueous dispersion, and the flexibility and smoothness of the conventional silicone finish are not so high. It was impossible to fully exert the feel of touch.

In the method for producing a polyester adhesive disclosed in JP-B-53-37920, an aromatic or dibasic acid is reacted with a glycol and a specific polyalkylene glycol. Even if the product is dropped into water, an aqueous dispersion of the polymer cannot be obtained, and cannot be used as various processing agents.

[0005] On the other hand, silicone resins such as polysiloxanes are also used as a treating agent and a touch control agent in various fields, but a block copolymer of polyester and polysiloxane is formed and dispersed in water. Although it is conceivable to use it for finishing processing such as fibers, it is expensive to make a copolymer, and when this is applied to fibers like amino silicon emulsion etc., the original water repellency of silicon appears Impairs the hydrophilicity and water absorption of cellulose-based fibers. In addition, when mixing polyester dispersion and silicone emulsion for use in dyeing finishing,
High shear such as forced agitation is added, and in those dyeing and finishing processes, the mixed silicone emulsion is broken, silicone is separated and oil floats on the surface of the processing liquid, causing oil spots such as fibers to be processed. It will make it dirty. As a result of intensive studies, the present inventors have solved these obstacles at once, and can be used in the form of an aqueous dispersion in various products, especially polyester molded products, and have a durable hydrophilicity and chargeability. It succeeded in obtaining the prevention properties and the excellent touch feeling obtained with silicone resin.

[0006]

That is, the present invention relates to a polyalkylene glycol represented by the following formula A, which represents an aromatic or aliphatic polyester or polyester polyether block copolymer (hereinafter referred to as "polyester"). Reaction products obtained by subjecting the aromatic or aliphatic polyester to a reaction product obtained by a transesterification reaction with an alkyl fatty acid ester of the formula (I) and one or more polyalkylene derivatives represented by the following formulas B, C, and D. It is a polyester-based reaction mixture composition containing the product. A: R ₁ COO (C _n H _2n O) _m H where n is an integer of 2 to 3, m is an integer of 4 to 20 and R ₁ is an alkyl group having 8 to 20 carbon atoms. B: (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _x [C
H ₃ Si (R ₂ -M) O] _y [CH ₃ Si (R ₃ -PO
A) O] _z Si (CH ₃ ) ₃ where POA is a polyalkylene glycol and M is —NH
_Two , R ₂ and R ₃ are an alkylene group having 1 to ₃ carbon atoms, and x is 5 to 2
An integer of 00, y is from 0 to 50, and z is an integer such that it is 10% by weight or more of the total weight of the polymer of the formula B. C: R ₄ O (C _n H _2n O) _m H where n is 2 to 3 An integer, m is an integer of 4 to 20, R ₄ is an alkyl group having 8 to 20 carbon atoms, D: H [O (CH ₂ ) _i ] _j H, where i is an integer of 2 to 5, and j is a total molecular weight of 200 ~
Any integer such as 8000.

In the present invention, examples of the polyester used include aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene polybutylene terephthalate, and aliphatic polyesters such as polyethylene succinate, polyethylene adipate and polybutylene adipate. And
Particularly, polyethylene butylene terephthalate polyester is preferred.

As the polyester polyether block copolymer used in the same manner as the above-mentioned polyester, a polyester obtained by reacting the above-mentioned polyester with a polyalkylene glycol such as polyethylene glycol and polybutylene glycol is used.

The polyoxyalkylene fatty acid ester of the above formula A to be reacted with the above polyester includes polyoxyethylene oleyl ester, polyoxypropylene oleyl ester, polyoxyethylene lauryl ester and the like. These are so-called surfactants, and may be selected from them and used.

These esters are considered to introduce a water-dispersible glycol functional group into the polyester by a transesterification reaction with the polyester, and are presumed to also react with other glycols. Further, it is considered that the unreacted fatty acid ester imparts water dispersibility to the produced polymer chains.

In order to react the polyoxyalkylene fatty acid ester of the formula A with the polyester, the reaction can be advanced by a trace amount of a polymerization catalyst and a trace amount of water remaining in the raw material polyester, but the reaction is further widely used. The polymerization may be advanced by adding a small amount of a polyester polymerization catalyst such as antimony trioxide.

Next, the polyalkylene glycol-modified silicone resin of the formula B will be described. The polysiloxane structure of the main chain preferably has a degree of polymerization of about 20 to 100. If the degree of polymerization is too large, the hydrophilicity decreases. Further, with respect to the R ₃ -POA group reacted therewith, R ₃ has 1 to 1 carbon atoms.
The alkylene group of 3, POA is a polyalkylene glycol, and polyethylene glycol, polypropylene glycol and polyethylene propylene glycol are usually used. The degree of polymerization must be at least 20 in order to improve the hydrophilicity, and z in the formula B is a number which is at least 10% by weight, preferably 40% by weight of the total weight of the polymer. Is good.

[0013] _-R 2 -M of _{R 2} is an alkylene group having 1 to 3 carbon atoms as described above, M is -NH ₂ group, either glycidyl group, -COOH group. However, these groups need not be present. That is, y may be 0.

The polyalkylene glycol-modified silicone resin of the above formula B is preferably a liquid which exhibits a liquid state at room temperature. Specifically, polyethylene glycol-modified silicone oil, epoxy polyoxyethylene-modified silicone oil, aminopolyoxyethylene-modified silicone oil There is oil etc.

[0015] Next described polyoxyalkylene alkyl ethers of formula C, _{R 4} is an alkyl group having 8 to 20 carbon atoms as described above, n represents 2-3 integer, m is 4 to 20 integer It is. This compound is also a nonionic surfactant, and examples thereof include polyoxyethylene lauryl ether, polyoxyethylene propylene lauryl ether, and polyoxypropylene alkyl ether.

Next, regarding the polyalkylene glycol of the formula D, i is an integer of 2 to 5, j is any integer such that the total molecular weight becomes 200 to 3000, and R ₆ is an ethylene group or a propylene group. And 1 has a molecular weight of 6
It is an arbitrary integer such as 00 to 3000, and specific examples include polypropylene glycol, polybutylene glycol, polyoxytetramethylene ether glycol, polyoxytrimethylene ether glycol, and the like.

The polyester and the polyalkylene glycol derivatives of the formulas A, B, C and D may be simultaneously added and reacted in a melt of the polyester, or after reacting the compound of the formula A, B, C, and D may be added and reacted. The ratio of the reaction is based on the formula A,
The mixture is melted and reacted so that the total amount of the polyalkylene glycol derivatives of B, C and D is 100 to 800% by weight based on the polyester. The reaction ratio of the polyalkylene derivative of the formulas A, B, C, and D is such that the polyalkylene glycol ester of the formula A is 1 to the above polyester.
0.00 to 300% by weight of the polyalkylene glycol-modified silicone resin of the formula B,
It is preferred to react by weight%. Other formulas A, C, D
The polyalkylene derivative may be appropriately added in consideration of the hydrophilicity of the reaction product.

The reaction is carried out by reacting the polyester with a glycol derivative such as a polyglycol-containing ester, a polyglycol ether, a polyalkylene glycol, or a glycol-modified silicone while keeping the polymer in a molten state in the presence of a catalyst for the polymerization of the polyester, for 250 to 290. The polyester is subjected to a transesterification reaction with an ester compound which is mixed and blended by reacting at a temperature of ° C. under a nitrogen stream. Further, alcoholysis occurs between a terminal hydroxyl group of a glycol derivative and an ester bond of the polyester, and the polyester is A glycol derivative of the polyester is formed with a slight reduction in molecular weight. As a result, a polyglycol, a silicone, and an alkyl group are introduced into the polyester, and at the same time, a carboxyl group and a hydroxyl group are introduced into the terminal of the product. This water-compatible reaction mixture composition is a resin composition that can be dispersed in water as described below, and can be dispersed extremely stably in water in the form of fine particles of nano-micron order. .

The polyester-containing composition thus reacted is melted and dropped into water or alkanolamine-containing water or silane-coupling agent-containing water to obtain an aqueous dispersion of a reaction mixture composition of the polyester.
The silane coupling agent is represented by the general formula XRSi (OR) ₃ . An example is shown below. As an amino-modified silane coupling agent, H ₂ NCH ₂ CH ₃ NHCH ₂ CH ₂ CH ₃ Si (OC
As H ₃ ) ₃ epoxy-modified silane coupling agent CH ₂ ＣＨCHSi (OOCH ₃ ) ₃ or the like as a vinyl-modified silane coupling agent. As an example of alkanolamine to be added to water, for example, the concentration of monoethanolamine or diethanolamine may be about 0.1 to 2% with respect to water, and effectively acts to finely disperse the reaction mixture. The optimum concentration of the silane coupling agent added to water is 0.1 to 5% based on water. The silane coupling agent reacts with the reaction terminal group of the reaction composition, stabilizes in water, and has an effect of improving affinity for an organic substrate.

In the polyester reaction, a heat stabilizer can be used to suppress the thermal decomposition of glycols, esters and ethers. Triazole and benzophenone compounds are effective.

An embodiment will be described below. Parts in Examples are parts by weight, and% means% by weight. Example 1 In a reaction vessel, a block copolymer resin of polyoxytetramethylene ether glycol and polybutylene terephthalate (Hytrel 3 manufactured by Du Pont-Toray Co., Ltd.) was used.
046) and 100 parts of polytetramethylene ether glycol (hereinafter abbreviated as PTMG. PT manufactured by Mitsubishi Chemical Corporation).
MG-2000) 30 parts, polyethylene glycol (hereinafter abbreviated as PEG; PEG-20 manufactured by Sanyo Chemical Industries, Ltd.)
00) 30 parts of 0.3 parts of zinc acetate and 13 parts of Irganox 13.
After adding 306 parts, the mixture was heated to 270 ° C. in a nitrogen stream.
The contents melted completely after about 10 minutes. The melt was mixed with polyoxyethylene lauryl ether (Sanyo Chemical Industries, Ltd.)
100 parts of Emulmin NL-100 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) and 20 parts of polyoxyethylene oleyl ester (EN-151 manufactured by Aoki Yushi Kogyo Co., Ltd.)
1) 45 parts and 10 parts of polyether-modified silicone (KF-351 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and added. The mixture is reacted at 270 ° C. for about 60 minutes,
A reaction mixture composition of the polyester was obtained. A 0.2% aqueous solution of monoethanolamine heated to about 50 ° C. was prepared so that the content of the reaction product became 15%, and the reaction mixture composition was dropped and dispersed while stirring. .

The obtained aqueous dispersion of the polymer was translucent white, and no precipitate was observed. When 5 parts of the dispersion was diluted with 100 parts of water, a blue fluorescent color was emitted. The particles of the dispersion were not visible to the naked eye, indicating that micro-dispersion had occurred.

[Example 2] Polytetramethylene terephthalate (Toraycon 5201X11 manufactured by Toray Industries, Inc.) 30
Parts, 40 parts of PTMG-2000, PEG-1000
30 parts and 0.02 part of antimony trioxide were mixed and melted at 270 ° C. for 30 minutes in a reactor under a nitrogen stream.

The melt was mixed with an epoxy polyether-modified silicone oil (X-22-3 manufactured by Shin-Etsu Chemical Co., Ltd.).
667) 40 parts, polyoxyethylene lauryl ether (Emulmin FL-100 manufactured by Sanyo Chemical Industries, Ltd.) 2
0 parts and 20 parts of polyoxyethylene oleyl ester (EN-1507 manufactured by Aoki Yushi Kogyo Co., Ltd.) were mixed and added, and the mixture was reacted at 260 ° C. for 20 minutes under a nitrogen stream.

The resulting polyester reaction mixture composition was added dropwise with stirring to warm water at about 40 ° C. containing 0.1% of an aminosilane coupling agent so that the resin composition became 10%. The dispersion of the reaction product after the addition of the resin was good, and a pale blue translucent dispersion was obtained. The 2% aqueous solution of this dispersion had a blue fluorescent color, and it was confirmed by a microscope that the reaction product was finely dispersed.

Comparative Example 1 An aqueous dispersion was prepared under the same conditions except that 10 parts each of the polyoxyethylene lauryl ether and the polyoxyethylene oleyl ester used in Example 2 were used. The amount of the ethylene derivative was small, it could not be dispersed, and a sediment of large white particles settled at the bottom of the container.

Example 3 A block copolymer resin of polyoxyethylene ether glycol and polyethylene terephthalate (STAFIX manufactured by Fuji Photo Film Co., Ltd.)
(P-LC) 140 parts, 200 parts of PTMG-1000,
150 parts of PEG-2000 were blended, heated to 270 ° C., and melt-mixed under a nitrogen stream for 80 minutes. 0.1 part of calcium acetate was mixed with the mixture, and 100 parts of polyoxyethylene lauryl ether (Emulmin NL-110) was further added.
Polyoxyethylene oleyl ester (EN-151)
1) 30 parts of an epoxy polyether-modified silicone (SF-84 manufactured by Dow Corning Toray Silicone Co., Ltd.)
21) 10 parts of an aminopolyether-modified silicone oil (BY-Dow Corning Silicone Co., Ltd.
16-893) 10 parts were mixed and added. Thereafter, the mixture was reacted at 270 ° C. for 40 minutes under a nitrogen stream to obtain a polyester reaction mixture composition.

This is a light yellow, transparent, high-viscosity rice cake-like mass. An aqueous solution at 50 ° C. containing 0.05% of an aminosilane coupling agent was added dropwise to the reaction product, followed by stirring. The reaction was successfully dispersed in water to give a translucent pale yellow dispersion.

Comparative Example 2 The same amount of the polyester polymer used in Example 3 was charged into a reaction vessel, and 0.1 parts of calcium acetate and 0.0 parts of antimony trioxide were similarly added thereto.
One part was mixed, heated to 270 ° C, and heated to 70 ° C in a nitrogen stream.
It was mixed and melted for minutes. Thereafter, PTMG- used in Example 3 was used.
1000 200 parts, PEG-2000 150 parts, polyoxyethylene lauryl ether 130 parts, epoxy polyether-modified silicone 10 parts, aminopolyether-modified silicone 10 parts were mixed and melted for about 5 minutes. The heated aqueous solution containing 0.05% of the aminosilane coupling agent was added dropwise with stirring. However, this drop had already separated in water and could not be successfully dispersed in water. The composition and heating conditions were almost the same as in Example 3, but it is considered that the solids were not dispersed in water because the polyester did not react with the glycol.

Example 4 120 parts of polyethylene glycol having a molecular weight of 1500 and lauryl alcohol ether of polyalkylene glycol (100 parts of polyethylene terephthalate resin chip for molding) (Sanyo Chemical Industries, Ltd.)
20 parts of Niroacty N-120) and polyethylene glycol oleyl ester (Eoki manufactured by Aoki Yushi Co., Ltd.)
N-1507) and 20 parts of polyether-modified silicone (KF-353 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and reacted at 270 ° C. for 3 hours under a nitrogen stream. The obtained reaction mixture composition was treated with aminosilane coupling agent 0.0
An aqueous solution containing 5% was added dropwise with stirring. The aqueous dispersion of this reaction product is a colorless and transparent aqueous solution and exhibits a fluorescent color.

5 parts of this solution was diluted with water to make 100 parts, thereby preparing a finishing processing solution. A polyester tricot and polyester / cotton (50/50) blended knitted fabric is immersed in the mixture, and excess liquid is squeezed out with a mangle.
It was dried at 0 ° C and heat set at 180 ° C for 30 seconds. The resulting knit and blend knit had a soft and slimy good texture. In addition, the original water repellency of polyester was improved by absorbing water droplets well.

COMPARATIVE EXAMPLE 3 A product obtained by reacting under the same conditions as in Example 4 except that 300 parts of polyethylene terephthalate was used, the oleyl ester of polyethylene glycol was not blended, and the other conditions were the same. Although dropped into the water containing the ring agent, the dispersion was broken shortly and the solid content was separated. It no longer disperses when re-stirred.

[0033]

The dispersion of the reaction product of the polyester containing the polymer type glycol-modified silicone thus obtained has a stable emulsion by forming the particles into fine spherical particles of the order of nanometers. Also, since this dispersion is mostly modified with nonionic compounds,
Even if a wide range of processing agents, including anionic and cationic, are mixed during the finishing of the fiber, the stability of the working fluid is not impaired. By finishing the fiber knitted fabric, the texture of the fiber can be made more flexible.
In particular, because polyester is the basic skeleton, mixed products including polyester fibers and their non-woven fabrics,
Good adhesion to synthetic paper, film, synthetic leather, etc., and good washing resistance due to the processing method. Further, the smoothness and slipperiness of the processed product are greatly improved.

Continued on front page F-term (reference) 4F056 AA01 CC01 CC44 CC48 FF07 FF10 FF20 4J031 AA49 AA53 AB04 AC03 AD01 AD03 AE15 AF03 AF16 4L033 AA02 AA07 AB05 AB06 AC04 AC06 AC07 AC09 BA08 BA14 BA21 BA22 BA96 CA46 AG4891G AH50 BE08 BE10 FA11 FA14 FA16 FA20 FA30

Claims (5)

[Claims] 1. An aromatic or aliphatic polyester or a polyester polyether block copolymer obtained by block copolymerizing the same with a polyalkylene glycol (hereinafter referred to as "polyester") and a polyalkylene glycol represented by the following formula A: A reaction product obtained by transesterification with an alkyl fatty acid ester of the above and the aromatic or aliphatic polyester were selected from one or more polyalkylene glycol derivatives represented by the following formulas B, C and D, respectively, and reacted. A polyester-based reaction mixture composition containing a reaction product. A: R ₁ COO (C _n H _2n O) _m H where n is an integer of 2 to 3, m is an integer of 4 to 20 and R ₁ is an alkyl group having 8 to 20 carbon atoms. B: (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _x [C
H ₃ Si (R ₂ -M) O] _y [CH ₃ Si (R ₃ -PO
A) O] _z Si (CH ₃ ) ₃ where POA is a polyalkylene glycol and M is —NH
_Two , R ₂ and R ₃ are an alkylene group having 1 to ₃ carbon atoms, and x is 5 to 2
An integer of 00, y is from 0 to 50, and z is an integer such that it is 10% by weight or more of the total weight of the polymer of the formula B. C: R ₄ O (C _n H _2n O) _m H where n is 2 to 3 An integer, m is an integer of 4 to 20, R ₄ is an alkyl group having 8 to 20 carbon atoms, D: H [O (CH ₂ ) _i ] _j H, where i is an integer of 2 to 5, and j is a total molecular weight of 200 ~
Any integer such as 8000. 2. The method according to claim 1, wherein the total amount of the polyalkylene glycol derivatives of the formulas A, B, C and D to be reacted with the polyester is mixed and melted so as to be 50 to 800% by weight based on the polyester. The polyester-based reaction mixture composition according to claim 1, which has been made. 3. The polyalkylene glycol to be reacted with the polyester is polyethylene glycol and polytetramethylene ether glycol, the total amount of which is 100 to 600% by weight based on the polyester, and the blending amount of polytetramethylene ether glycol. Is 0 to 500% by weight based on the amount of polyethylene glycol
3. The composition according to claim 1, wherein the mixture is melted and reacted.
The polyester-based reaction mixture composition described in 1. 4. The method according to claim 1, wherein the polyester-based reaction mixture composition according to claim 1 is melt-mixed with water, alkanolamine-containing water or silane coupling agent-containing water. An aqueous dispersion containing a polyester-based reaction mixture composition. 5. A fiber finishing agent comprising the polyester-based reaction mixture composition according to claim 1.