KR101183517B1 - Urethane Arcylate, Binder Composition Containing the Composition, and Fabric Treatment Method Using the Binder - Google Patents

Abstract

The present invention relates to a novel urethane acrylate, a binder composition comprising the same, and a method for processing fibers using the same. According to the processing method of the fiber using the UV curable binder of the present invention, it is possible to prevent fiber damage due to heat, so that even after the processing agent is fixed to the fiber, the inherent properties of the fiber can be maintained and the shape stability can be maintained. . The processing method of the fiber of the present invention is possible by simply irradiating with UV, so there is no risk of environmental pollution or adverse effects on the human body, and it does not require a high temperature heat as well as occupy less installation area than a conventional thermosetting device. Therefore, it is possible to improve the laundry durability of the more economical and particularly volatile aroma capsules.

Description

Urethane acrylate, Binder composition comprising same and fiber processing method using same {Urethane Arcylate, Binder Composition Containing the Composition, and Fabric Treatment Method Using the Binder}

The present invention relates to a novel urethane acrylate, a binder composition comprising the same and a fiber processing method using the same.

It is the goal of the fiber chemist to make durable aroma processing on the fiber, but since the fragrance material is volatile, it must be micro (nano) encapsulated to attach to the fiber for a long time. Since there is no affinity between the encapsulated aroma and the fiber, it must be cured with a fixing agent. The curing process is a process for several minutes at 130-170 ° C, and the aromatic aroma in the capsule is rapidly lost from the capsule due to evaporation, expansion or destruction. At the same time as the aromatic aroma in the fiber is reduced, the durability of fragrance processing is also reduced. Efforts have been made to cure by UV irradiation at low temperatures as a means to cure the aromatic processing agent to the fiber in place of the high-temperature processing heat curing.

The development of UV curing processing technology for textiles is a future state-of-the-art dyeing and processing technology that can significantly reduce energy consumption and wastewater generation. ① Thermal drying. Productivity is good because the curing time is shorter than that of heat curing. ② It is a low-volume environment-friendly resin because of less volatile materials. ③ Especially, UV curing requires a compact equipment and requires a small area. The advantages of the small ones, but on the contrary, ① the unit cost is higher than the conventional resin composition of the thermosetting type, ② the rapid curing in a short time from the state of relatively small molecular weight has a large number of crosslinking point, and because of the shrinkage of the cured product due to large curing shrinkage Poor adhesion is likely to occur, ③ cause skin irritation by using solvent. In particular, when applying a UV curing agent to the fibers conventionally used in paints, inks, electronic materials, these disadvantages are more highlighted. There is a need for a study on a processing method using UV curing to provide a fiber having excellent binder properties without impairing the physical properties of the fiber.

The present invention aims to provide a novel urethane acrylate to solve the above problems.

The present invention also relates to a UV curable binder containing the urethane acrylate.

In addition, an object of the present invention is to provide a fiber having excellent binder properties by applying the binder to the fiber without damaging the physical properties.

The present invention relates to novel urethane acrylates. More specifically, it relates to the urethane acrylate represented by the following formula (1).

In Formula 1,

L is an integer of 1 to 6, m and n are each an integer of 1 to 10, R represents a hydrogen atom or a methyl group, D represents a divalent group selected from an aliphatic ring and an aromatic ring, and M represents a polytetramethylene glycol A hydrophobic divalent group derived from G represents a poly (ethylene glycol) or a hydrophilic divalent group derived from poly (ethylene glycol) (propylene glycol).

The present invention also relates to a binder composition comprising 100 parts by weight of the urethane acrylate, 1 to 4 parts by weight of photoinitiator and 2 to 5 parts by weight of crosslinking aid.

The present invention also relates to a method for processing fibers, comprising the step of printing the binder on the fiber sample, and curing the binder on the surface of the fiber sample by irradiating the printed fiber sample with UV.

According to the processing method of the fiber using the UV curable binder of the present invention, it is possible to prevent fiber damage due to heat, so that even after the processing agent is fixed to the fiber, the inherent properties of the fiber can be maintained and the shape stability can be maintained. . The processing method of the fiber of the present invention is possible by simply irradiating with UV, so there is no risk of environmental pollution or adverse effects on the human body, and it does not require a high temperature heat as well as occupy less installation area than a conventional thermosetting device. Therefore, it is more economical and can improve the durability of the aroma capsule.

1 is an FT-IR result of the urethane acrylate prepared in Preparation Example 1.
Figure 2 is a scanning microscope (SEM) photograph of the fiber printed with a UV curable binder according to the present invention.
3 is a graph of the content of the residue flavor oil for each binder according to the number of washing.

Hereinafter, the present invention will be described in more detail.

The present invention relates to novel urethane acrylates. More specifically, it relates to the urethane acrylate represented by the following formula (1).

[Formula 1]

In Formula 1,

L is an integer of 1 to 6, m and n are each an integer of 1 to 10, R represents a hydrogen atom or a methyl group, D represents a divalent group selected from an aliphatic ring and an aromatic ring, and M represents a polytetramethylene glycol A hydrophobic divalent group derived from G represents a poly (ethylene glycol) or a hydrophilic divalent group derived from poly (ethylene glycol) (propylene glycol).

D in Chemical Formula 1 is 4,4'-methylenediphenyl diisocyanate (MDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), m-tetramethylxenyl diisocyanay (TMXDI), or More preferably, it is a divalent group derived from 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI).

Hydrophobic divalent and hydrophilic divalent groups of Formula 1 is preferably a number average molecular weight of 500 ~ 4,000.

It is preferable that the ratio of m and n of the said Formula (1) is 1: 1-10. If out of the above range, there is a problem that the adhesiveness of the binder containing the urethane acrylate is poor.

Finally, the urethane acrylate preferably has a number average molecular weight of 5,000 to 20,000. If the number average molecular weight of the urethane acrylate is less than 5,000, there is a problem that can not be applied to the fiber treatment due to the low viscosity of the binder containing it, if the excess exceeds 20,000 may cause a problem of hardening when synthesized due to high viscosity Because there is.

The urethane acrylate is a hydrophilic polyol such as poly (ethylene glycol) or poly (ethylene glycol) (propylene glycol), hydrophobic polyol such as poly tetramethylene glycol, and the like and isocyanate isocyanate such as IPDI, TMXDI or H ₁₂ MDI. It can be prepared by reacting the reactor.

In addition, the present invention relates to a binder including 1 to 4 parts by weight of the photoinitiator and 2 to 5 parts by weight of the crosslinking assistant with respect to 100 parts by weight of the urethane acrylate of the formula (1).

The binder may be adjusted to a viscosity of 10,000 to 30,000 cps using a solvent such as water. By mixing the binder and the aromatic capsule, fragrance processing is possible. When adding an aromatic capsule, it is preferable to mix 1 to 5 parts by weight with respect to 100 parts by weight of urethane acrylate.

The photoinitiator is excited when UV is irradiated to generate radicals or ions to initiate photopolymerization or to cause photopolymerization with the aid of other sensitizers, preferably a benzophenone-based compound, an acyl phosphine oxide compound, or an acetophenone-based compound. At least one selected from the group consisting of compounds and benzoin ether compounds is suitable. Preferably 2-hydroxy-2-methylpropionphenone, 1-hydroxy cyclohexyl ketal, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide and the like can be used, more preferably 2 -Hydroxy-2-methylpropionphenone and diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide can be used in combination.

The photoinitiator is used 1 to 4 parts by weight based on 100 parts by weight of the compound of the formula (1) urethane acrylate. In this case, when the content of the photoinitiator is less than 1 part by weight, the degree of curing decreases and the binder property deteriorates.

The crosslinking aid serves to increase the binder property and to control the viscosity of the binder and to use a monomer including diacrylate. Preferably, silicone acrylate, polyethylene glycol (PEG) 400 diacrylate, or the like is used, and more preferably polyethylene glycol (PEG) 400 diacrylate is used.

The crosslinking aid is used 2 to 5 parts by weight based on 100 parts by weight of the compound of the formula (1) urethane acrylate. Less than 2 parts by weight does not act as a crosslinking aid, and more than 5 parts by weight reduces the performance of the binder.

The present invention also relates to a method for processing fibers comprising the step of printing the binder on the fiber, and curing the binder on the surface of the fiber by irradiating the printed fiber with UV.

At this time, the fibers used are not particularly limited, both natural fibers and synthetic fibers can be used, woven fabrics, knitted fabrics and non-woven fabrics may also be subject to the binder treatment.

UV is an electromagnetic wave having a wavelength shorter than visible light, and can not only cut and oxidize molecular bonds of the irradiated surface organic material depending on the irradiation wavelength but also easily polymerize and crosslink the photocurable monomer.

The emission of UV is achieved by heating a substance having an atomic structure that is easy to emit electromagnetic waves to vaporize and applying a large amount of energy from the outside. Typically, mercury lamps are used a lot. When a mercury gas atom receives energy, mercury electrons are excited, and then the electrons return to a stable state to emit invisible UV. In general, UV lamps are divided into sterilization and UV curing, and are used in various ways depending on the intensity and wavelength range of the emitted energy.

In the fiber processing method using UV curing, the UV curing mechanism can be largely divided into radical reaction and cationic reaction. In the case of the radical reaction, the photoinitiator included in the processing agent is activated by UV to generate free radicals, which in turn activate the reactive oligomer to form a huge network structure, and then the curing reaction is terminated through a stop reaction. Machining is completed.

In the present invention, the fiber sample is printed with the UV-curable binder and then dried for 1 to 10 minutes at 50 to 100 ° C. Through the drying process, the efficiency of the curing reaction can be further improved.

At this time, the printing is printed using a silk screen, the printing thickness is preferably 10 to 30 ㎛. If the printing thickness is less than 10 μm, the amount of binder added is low, and the adhesiveness is lowered. If the printing thickness is more than 30 μm, the feel of the fiber may be stiff due to the excess binder and the film may be broken. This printing thickness can be controlled by adjusting the viscosity of the binder.

In particular, the printing amount of the binder when printing the binder according to the present invention on the fiber is preferably 10 to 20 g / m ² , there is a problem in the physical properties and feel outside this range.

Thereafter, UV is irradiated to the dried sample using a UV irradiator. It is preferable to use a metal halogen lamp or a gallium lamp whose main wavelength is UV-A region for UV irradiation for hardening of a processing agent.

The amount of UV radiation affects the adhesion of the fiber, preferably irradiated in the range of 0.5 to 2 J / cm ² , more preferably in the range of 1.0 to 1.5 J / cm ² . If it is less than 0.5 J / cm ^2, the activation of the photoinitiator is not made well, the progress of the curing reaction is not active, there is a problem that the adhesion is inferior, when exceeding 2 J / cm ² fibers are embrittled.

Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto.

Experimental Example  One: NCO  Measure

2-3 g of the sample was taken in a 250 ml Erlenmeyer flask. 25 ml of toluene was added to dissolve (isopropanol can be used when not dissolved in toluene). A 20 ml pipette of 2N n-dibutylamine ([CH ₃ (CH ₂ ) ₃ ] 2 NH = 129.25,1 L, Assay: 99%) solution was added. After standing for 15-20 minutes, 100 ml of isopropanol was added to the measuring cylinder. After adding about 5-10 drops of Bromocresol green indicator, titration was started with 1N aqueous hydrochloric acid solution. 2 g Brocresol Green (C ₂₁ H ₁₃ Br ₄ O ₅ SNa = 720: Name of reagent) was dissolved in ethanol to make 100 ml. A blank test was performed at the end of the transition from blue to yellow.

[Equation 1]

NCO% = [(A-B) x F x 4.2] / S

A: Amount of 1N aqueous hydrochloric acid solution

B: amount of 1N aqueous hydrochloric acid solution

F: concentration coefficient of 1N hydrochloric acid aqueous solution

S: sample weight (g)

Experimental Example  2 : Laundry resistance ( KS  K 0640 A-2)

KS K 0640 A-2 Washing conditions to determine whether the fragrance oil is released slowly. To quantify the fragrance remaining after washing, cut cotton fiber treated to a certain size and extract it with ethanol for a day. Absorbance was measured by UV-VIS spectroscopy at 285 nm, 290 nm jasmine oil). Abs is the absorbance of the fragrance oil eluted before and after washing.

% Of residue fragrance oil = Abs _{after washing} / Abs _{before washing} X 100

Manufacturing example  1: urethane Acrylate  Produce

The 500 ml 4-neck flask was equipped with a mechanical stirrer, a condenser with a drying tube, a thermometer and a nitrogen injector. The mounted flask was placed in a mantle and the flask was first heated in vacuo to remove residual moisture. Polytetramethylene glycol (PTMG, Polytetramethylene glycol, Mn 500 to 2,000) and polyethylene-propylene glycol (PEG / PPG, Polyethylene glycol / Polypropylene glycol, Mn 500 to 2,000) were weighed in a 1: 1 molar ratio and then charged into a flask. After mixing all the polyols at 90 ℃ and cooled to 60 ℃ and dissolved in DMBA (Dimethylol butyric acid). Methylene diphenyl diisocyanate (MDI) containing 0.1% (w / w) catalyst (dibutyl tin dilaurate) was slowly added dropwise (the exothermic reaction), and when the dropwise addition was completed, the temperature was raised to 75-80 ° C. After measuring the NCO content from 2 hours after the increase in temperature (4-5%) when the expected content was introduced to the acrylic reactor (2-HEMA, 2-HEA, Glycidol) to cool to 50 ℃ and capping the NCO end. Reaction progress was confirmed by NCO measurement or FT-IR [see FIG. 1]. Upon completion of the reaction, triethylamine diluted with water was added dropwise and neutralized at 50 ° C. for 1 hour. The concentration was adjusted to 30 to 40% solids.

To prepare a urethane acrylate represented by the formula (2) (number average molecular weight about 15,000);

In Formula 2,

L is 1, m and n are each an integer of 1 to 10, R represents a hydrogen atom or a methyl group, D represents a divalent group selected from methylene diphenyl diisocyanate, and M represents a poly of number average molecular weight 500 to 2,000 Hydrophobic divalent group derived from tetramethylene glycol is shown, G shows the hydrophilic divalent group derived from poly (ethylene glycol) or poly (ethylene glycol) (propylene glycol) of the number average molecular weights 500-2,000.

FT-IR analysis of the prepared urethane acrylate is shown in FIG.

Example  1: Manufacture and processing of binders of fibers

Photoinitiator which mixed 100 g of urethane acrylate which is the compound manufactured by the said preparation example 1, 2-hydroxy-2-methylpropionphenone, and diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide in 3: 1 4 g and 5 g of diacrylate made of polyethylene glycol (PEG) 400 as a crosslinking aid, and 2 g of commercially available micro (nano) aroma capsules were added thereto to prepare a binder adjusted to a final viscosity of about 25,000 cps with water.

As a sample to be treated with binder, a refined bleached 20 male cotton fabric was cut into 30 cm × 20 cm size and silkscreen printed with the diluted binder.

The printed sample was dried at 80 ° C. for 2 minutes, and then irradiated with UV with a irradiation amount of 1.1 J / cm ² using a UV curing machine equipped with a metal lamp (Fe).

Evaluation of the wash durability of the aroma capsule processed fiber sample was measured by the method of Experimental Example 2.

Whether the binder is processed Residue after 1 wash
% Of fragrant oil Processing (1.1 J / cm ² UV irradiation) 75 Untreated 0

Example  2: according to the molecular structure of the binder Tensile strength  Measure

Fiber processing was performed in the same manner as in Example 1, but the tensile strength of the urethane acrylate synthesized by varying the type of isocyanate was measured by KS K 0531 method and shown in Table 2 below.

Name of sample Isocyanate Alkyl fatty acids F of Formula 2 The tensile strength
kgf / mm ² UAI-PEG IPDI DMBA Poly Tetramethylene-Ethylene-Glycol 0.8 UAI-PEG / PPG IPDI DMBA Polytetramethylene-ethylene-propylene glycol 1.2 UAT-PEG / PPG MDI DMBA Polytetramethylene-ethylene-propylene glycol 1.5 UAH-PEG / PPG H ₁₂ MDI DMBA Polytetramethylene-ethylene-propylene glycol 0.9

Tensile strength was significantly different according to the change of molecular structure, and the viscosity was not increased and the tensile strength was high when reacting with MDI (4,4'-Methylene diphenyl diisocyanate) among three isocyanates.

Example  3: Printing film  According to thickness Residue Fragrant oil  Content measurement

The water resistance was measured by adjusting the thickness of the printing film while varying the viscosity of the diluted concentration binder by adjusting the amount of water added in the binder, which is shown in Table 3 below.

Viscosity of binder (cps) Printing film thickness (㎛)
(Measured with a colorimeter) Residue after 10 washes
% Of fragrant oil touch 20,000 20 25 ○ 23,000 32 30 ○ 26,000 40 37 △ 30,000 50 42 △

As shown in Table 3, as the printing film thickness increases, the adhesion is improved, but when the thickness of the printing film exceeds 30 μm, the fibers were stiff and the touch was poor.

Comparative example  1: acrylic binder

After printing the aromatic capsule using a commercially available acrylic screen binder (Korean Patent No. 520410) for 2 minutes at 150 ° C., the content of the residue flavor oil is shown in Table 5 below. The acrylic binder had excellent initial adhesiveness but poor touch, and the content of the residue aroma decreased drastically with the number of washes.

Comparative example  2: polyurethane binder

After printing the aromatic capsules using a commercially available silk binder for polyurethane screen (Korean Patent No. 249728), the content of the residue flavor oil is shown in Table 4 below.

Washing count Example 1
Urethane Acrylate Comparative Example 1
Acrylic Binder Comparative Example 2
Polyurethane binder 1 time 75 90 60 5 times 55 50 30 10 times 30 20 15 20 times 10 5 5

As can be seen in Table 4, the initial adhesiveness of Comparative Examples 1 and 2 was excellent, but it was confirmed that such adhesive performance was significantly reduced depending on the number of washing. Therefore, when the fiber is treated using the binder containing the urethane acrylate of the present invention was confirmed that the effect of fiber treatment lasts for a long time even washing the fiber.

Claims (16)

Urethane acrylate represented by following formula (1).
[Formula 1]

In Chemical Formula 1,
L is an integer from 1 to 6, m and n are each an integer from 1 to 10, R represents a hydrogen atom or a methyl group, D is 4,4-methylenediphenyl diisocyanate (MDI), isophorone diisocyanate ( IPDI), toluene diisocyanate (TDI), m-tetramethylxenyl diisocyanai (TMXDI), or divalent group derived from 4,4-dicyclohexylmethane diisocyanate (H ₁₂ MDI), M is Hydrophobic divalent group derived from polytetramethylene glycol is represented, G represents a hydrophilic divalent group derived from poly (ethylene glycol) or poly (ethylene glycol) (propylene glycol).
delete The urethane acrylate according to claim 1, wherein the hydrophobic divalent group and the hydrophilic divalent group have a number average molecular weight of 500 to 4,000.
The urethane acrylate according to claim 1, wherein the ratio of m and n is 1: 1 to 10.
The urethane acrylate of claim 1, wherein the urethane acrylate has a number average molecular weight of 5,000 to 20,000.
100 parts by weight of the urethane acrylate of any one of claims 1 and 3 to 5;
1 to 4 parts by weight of photoinitiator; And
2 to 5 parts by weight of a monomer containing diacrylate as a crosslinking aid;
Binder composition comprising a.
The binder composition according to claim 6, wherein the binder further comprises 1 to 5 parts by weight of the aromatic capsule based on 100 parts by weight of the urethane acrylate.
The binder composition of claim 6, wherein the binder has a viscosity of 10,000 to 30,000 cps.
The binder composition of claim 6, wherein the photoinitiator is at least one selected from a benzophenone compound, an acyl phosphine oxide compound, an acetophenone compound, and a benzoin ether compound.
10. The binder composition of claim 9, wherein the photoinitiator is a mixture of 2-hydroxy-2-methylpropionphenone and diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide.
delete The binder composition of claim 6, wherein the crosslinking aid is polyethylene glycol (PEG) 400 diacrylate.
Printing the binder of claim 6 on a fiber; And
UV irradiation of the printed fiber to cure the binder on the fiber surface
Processing method of the fiber comprising a.
The method according to claim 13, wherein the fiber is dried with a UV-curable binder and then dried at 50 to 100 ° C. for 1 to 10 minutes.
The method of claim 13, wherein the printing thickness of the binder is 10 to 30 ㎛.
The method of claim 13, wherein the UV is 0.5 to 2 J / cm ² .

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