KR101956469B1 - Method for constructing eco-friendly adhesive coating layer of fiber re-adhesive product with high performance initial adhesive force and re-releasability - Google Patents

Abstract

The present invention relates to adhesive layer materials and a compounding process, which have a strong initial adhesive strength on the back side of a printable textile products and have a backside adhesive layer which maintains the adhesive strength even when being reattached. An adhesive coating layer is manufactured by forming an adhesive surface on the back side of a woven or knitted fabrics, and perform a coating process by diving into a primary coating using a PU resin and a secondary coating using an acrylic resin, and based on the weight (100) of the PU resin and the acrylic resin, each of 2.5% of dispersant, 1.5% of a surface modifier, 2.5% of a leveling agent; 1% of a slip agent; and 0.5 of an antibacterial agent are included to perform the coating process.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for constructing an eco-friendly adhesive coating layer of a fiber re-adhesive product having high initial adhesion and re-

The present invention relates to a fiber-printed product having a back pressure-sensitive adhesive layer having a strong initial pressure-sensitive adhesive strength and a maximum adhesive force even upon reattachment, and more particularly to a material and a blending process for constituting the pressure-sensitive adhesive layer.

As is well known, advertisements, interior products, fancy products, etc. used for printing images have been expanded to textile products that are woven or knitted from conventional paper printing paper.

For example, fiber re-printing paper such as the following prior art documents has been introduced, but one of the main functions required for such a fiber re-printing paper is to repeatedly perform the adhesion force to adhere to the object to be attached and the re- The adhesive force of the conventional product is excessively strong at the initial stage and has a problem that the adhesive force is rapidly deteriorated in repeated attachment and detachment.

On the other hand, like 3M's 'post-it', it has been repeatedly attached to the surface of paper material repeatedly. However, even if the position is changed, a function having a certain level of adhesive strength has been applied to the product. However, It is difficult to directly apply the adhesive component and the application method used in general paper in consideration of the weight of the paper, the unevenness of the surface, and the characteristics of the material.

Patent Publication No. 10-2003-0028917 (Apr. Patent Publication No. 10-2003-0091864 (2003.12.03)

The present invention, which is devised in view of the problems and necessity of the conventional fiber re-printing paper, is to select an adhesive capable of exhibiting optimum physical properties in order to improve adhesive strength, and to provide an adhesive capable of maintaining adhesive strength even after re- It is possible to select the additives that can improve the reliability problem, to select the hardening agent that can maintain the dimensional stability, the hardening agent according to the input of the hardening agent versus the productivity, and the hardening agent to improve the workability and productivity. In order to improve the adhesive property, It is aimed to develop blending technology.

     The objective of this research is to develop the coating process technology that can exhibit optimum physical properties and to establish process conditions for the coating process.

In order to accomplish the above object, the present invention provides a method for producing a woven or knitted fabric, comprising the steps of: forming a pressure-sensitive adhesive surface on a back surface of a woven or knitted fabric as a fiber material, , And the coating and the secondary coating are each coated with a dispersing agent, a surface modifying agent, a leveling agent, a slipping agent, and an antimicrobial agent, and dried . (PU) resin and an acrylic resin are contained in an amount of 100% by weight based on 100% by weight of a dispersant, 1.5% of a surface modifier, 2.5% of a leveling agent, 1% of slip, and 0.5% of an antimicrobial agent.

According to the present invention, it is possible to provide a textile printing product having a strong initial adhesive force and a backside adhesive layer which maintains the adhesive strength even when reattached, thereby providing a commercial product, an interior product, a fancy product , Which will lead to the development of various types of superior trend products.

Figure 1 shows the coating process of the present invention
2 is a cross-sectional view of a textile article according to the present invention

Hereinafter, embodiments of the present invention will be described in detail.

(1) Selection of adhesives and additives according to product characteristics

Resin materials for adhesion improvement were selected and evaluated.

  1) Water-soluble urethane resin (PUD)

The aqueous polyurethane resin is classified as follows according to its shape and manufacturing method.

 - classification by emulsification method

  (A) Forced dispersion type - When dispersing the PU prepolymer in water, a method of dispersing at high speed using an external emulsifier

  (B) Self-emulsifying type - Ionic center is introduced into the main chain of PU prepolymer to disperse in water

     ① Anion type - polyurethane Prepolymer with anion center such as DMBA introduced into the main chain

     ② Cation type - Polyurethane Prepolymer having cation center such as MEDA introduced into the main chain of the prepolymer

     ③ Non-ionic-polyurethane Prepolymer that has a nonionic center such as PEG introduced into the main chain of the prepolymer.

   (C) Classification according to resin manufacturing process

Synthesis method Contents Acetone
Process Prepolymer is synthesized using low boiling solvent (Acetone).
How to make PUD by dispersing in water.
Acetone used in the synthesis was removed by distillation under reduced pressure. Hot-Melt
Process Capping NCO-terminated prepolymer with Urea at high temperature.
Dispersed in water and condensed with Formaldehyde and Urea
The way of bridging. Prepolymer
Mixing
Process NCO-terminated prepolymer containing Ionic centers such as DMBA
And neutralized with neutralizing agent and dispersed in water.
The unreacted NCO at the terminal is chain extended by polyamine.
(A small amount of solvents such as DMF and NMP may be used in preparation of the prepolymer) Supporter
Process The water dispersion of the dispersed NCO end is chain-extended with Blocked Amine
system

- Selection of raw materials

 The raw materials are mainly 1) polyol, 2) glycol and amine, 3) isocyanate, 4) solvent, and 5) additives.

- Raw materials for pud synthesis

 1) Types and characteristics of polyols.

 Chemical name Cold resistance Water resistance Heat resistance Mechanical
Property  Polyether series  PEG: Polyethylene glycol ◎ X ○ ○  PPG: Polypropylene glycol ◎ ◎ △ △  PTMG: Polytetramethylene glycol ◎ ◎ ○ ○  Polyester system  PEP: Polyester polyol △ △ ◎ ◎  Carbonate system  PCD: Polycarbonatediol △ ◎ ◎ ◎  Caprolactone series  PCL: Polycaprolactone glycol ◎ ○ ◎ ◎

2) Diol and Ionic center

 Chemical name Remarks Diol
(Chain extender)  EG: Ethylene glycol  1.4 BD: 1,4-Butane diol  1.6 HD: 1,6-Hexane diol  NPG: Neopentyl glycol Ionic center
(Emulsifier)  DMPA: Dimethyl propionic acid Anion  DMBA: Dimethyl butylic acid  MEDA: N-methyl diethanol amine Cation  Ethoxylated copolymer Nonion

  3) Neutrilizer

 Chemical name Remarks corrector  TEA: Triethyl amine  For anion neutralization  HCl: Hydrocholic acid  Cation neutralization  AAc: Acetic acid  PAc: Phospholic acid

4) Polyisocyanate

 Chemical name Remarks Yellow type
(Aromatic)  TDI: Toluene diisocyanate  MDI: 4,4-Diphenylmethane diisocyanate Non-yellowing type
(Aliphatic or
Alicyclic)  HDI: 1,6-Hexamethylene diisocyanate  IPDI: Isophorone diisocyanate  H12MDI: 4,4-Dicyclohexylmethane diisocyanate

5) Solvent

 Chemical name Remarks  Act: Acetone  Used for Acetone (ketone) Process  MEK: Methylethyl ketone  DMF: Dimethyl formamide  Applied to Prepolymer Mixing Process  NMP: N-methyl-2-pyrolidone

6) Amine Chain extender & Cross-linking agent

 Chemical name Remarks  Chain extender (bifunctional)  EDA: Ethylene diamine  HMD: Hexamethylene diamine  PPRZ: Piperazine Anhydrous  Cross-linking agent (trifunctional)  DETA: Diethylene triamine  Cross-linking agent (tetrafunctional)  TETA: Triethylene tetramine

  7) Other additives

 Chemical name Remarks Antioxidant
(Antioxidant) IRGANOX 1010: Pentaerythrityl-tetrakis [3- (3,5-
di-t-butyl-4hydroxyphenyl) propionate] UV absorbers / stabilizers
(UV Absorb
& Stabilizer) TINUVIN P: 2- (2-Hydroxy-5-methyl-phenyl) -
2H-benzotriazole ZIKASORB: N-4-Ethoxycarbonylphenyl) -N'-
methyl-N'-phenylformamidine  Defoamer  SN-DEFOAMER 399: Modified Silicone series Leveling agent
(Leveling agent)  Polyether-modified dimethylsiloxane  Thickener Hydrophobically modified ethoxylate urethane
copolymer Aqueous hardener
(Curing agent)  NCO curing agent (used for HDI trimer, two-part adhesive)  Other  Slip agent, Wetting agent, Surface hardener, Toner, etc.

- Hardening condition according to hardening accelerator at the time of PUD sample min.

Drying time (70 * 1 hr)
Remarks Reaction promoter 0.2P 0.5P 1.0P TEDA 60 80 82
MI 65 85 86

Product Name Drying conditions Curing condition Remarks
℃
sec 110 130 150 ℃
sec 110 130 150
Company H
60 ○ ◎ ◎ 60 △ ○ ○

180 ◎ ◎ ◎ 180 ○ ○ ◎ 300 ◎ ◎ ◎ 300 ○ ◎ ◎

As a result, the water - soluble polyurethane has a considerably long curing condition, which makes it difficult to control the tacky property, and difficulty in imparting tackiness.

It has been found that it is difficult to select a suitable pressure-sensitive adhesive for this product because the adhesive property is easy to express rather than the property of the pressure-sensitive adhesive. Therefore, water-soluble polyurethane is excluded.

2) Water-soluble acrylic resin

- Difference between adhesion and adhesion

Adhesion: Adhesion is a state in which a solid surface of the same kind or a different kind is adhered to a surface and adhered to each other.

Adhesion: bonding of an object and an object is a type of adhesive, which can be temporarily adhered, adhered at room temperature with a small pressure for a short time, and has cohesive force and elasticity.

adhesive Solid (dendritic) semifluid Liquid Elastic property Viscoelastic property Viscous property

Adhesion: Adherence due to viscosity property

Adhesion: Adhered by elastic properties

- Pressure Sensitive Adhesives (PSA)

; Adhesion is used almost the same as adhesion, but it is classified according to its use.

- Basic raw materials of acrylic adhesive

 Representative monomers used in acrylic pressure-sensitive adhesives

Monomer Tg (占 폚)
Characteristic Abbreviation designation Main monomer 2-EHA Ethylhexyl acrylate -70 General-purpose main monomer, Tacky, low-temperature characteristics BA Butyl acrylate -55 Universal main monomer 2-MEA Methoxyethyl acrylate -50 Hydrophilic monomer


Comonomer VAc Vinyl acetate 32 General purpose hard monomer, price ↓,
Cohesion AN Acrylonitrile 97 Cohesion St Stechlen 80 Cohesion,
It is difficult to copolymerize with acrylic. MMA Methyl methacrylate 105 Cohesion, Tackiness Control EA Ethyl acrylate -22 The smell is strong. MA Methyl acrylate 8 The smell is strong. Hydrophilic, cohesive, heat-resistant

Functional monomer MAA Methacrylic acid 228 adhesiveness AA Acrylic acid 106 Adhesion, crosslinking origin IA Itaconic acid Adhesion, crosslinking origin HEMA Hydroxyethyl methacrylate 55 Crosslinking origin HEA Hydroxyethyl methacrylate -15 A crosslinking starting point,
Acryl and good copolymerization DM Dimethyamine ethyl methacrylate 13 Emulsion-free, cohesive powerless emulsifier AM Acrylamide 165 Cohesion,
It is difficult to copolymerize with acrylic. PEA Phenoxy ethyl acrylate -22 Imparting cohesive force, imparting heat resistance,
Refractive index adjustment N-MAM Methylol acrylamide Self-conformity GAM Glycidyl methacrylate Crosslinking origin, thermal reactivity AAEM Acetoxyacetoethylmethacrylate 5 Adhesion, noncorrosive Maleic anhydride Adhesion, crosslinking origin

- Types and Characteristics of Polymerization

Type of polymerization
Characteristic

Bulk polymerization

(bulk polymerization)
  Monomer + initiator - Pure Polymers

- difficulty in controlling heat generation
Solution polymerization

(Solution Polymerization)   Monomer + initiator + solvent - Easy heating control

- Easy to manufacture

- solvent pollution problem

Emulsion polymerization

(Emulsion Polymerization)

Monomer + initiator + water + emulsifier

- Easy heating control

- Polymeric materials

- Additives → Decrease in physical properties

Suspension polymerization

(Suspension Polymerization)

Monomer + initiator + water + dispersant

- Easy heating control

- Polymeric materials

- washing, drying process

Other

(UV, EB Radiation)
Oligomer + photoinitiator + diluent
- Fast curing

- Acrylic adhesive

Polymer for adhesive needs fluidity at room temperature, lowering glass transition temperature

The number of carbon atoms of the alkyl group is about 4-10, the use of acrylic acid acrylate copolymer

Tg minimum in C8

: Increase of carbon number of steric alkyl group, difficulty of chain approach of polymer, easy movement of polymer chain, decrease of Tg

  Time change relationship of adhesive force

- Based on the theoretical part above, sample H obtained from company H and conducted the acrylic resin test.

TEST
matter One 2 3 4 5 Company H
Acrylic resin 100 100 100 100 100 Viscosity (cps) 3,500 3,500 3,500 3,500 3,500 Drying conditions (占 폚 SEC) 100 x 10 100 x 20 100 x 30 100 x 40 100 x 50

Result at TEST

TEST
Properties One 2 3 4 5 This form × (sticky) × (sticky) × (sticky) △ △ Morphological stability × × × △ △ Stickiness ○ ○ ○ × × Bubble property × × × × △

- Based on the above results, it is considered that acrylic resin suitable for the characteristics of the product which has the initial adhesion and easy to move the attachment surface is considered to be suitable as acrylic resin.

○ In order to compensate the problems during testing or working, the following additives were selected.

- Introduce defoamer to improve bubble generation during operation.

- Introduced dispersant to spread evenly and improve dispersibility of resin.

- Introduced a leveling agent to improve the uniformity of the film due to the adjustment of the surface tension.

- Introduced slip for ease of riding.

- Add antibacterial agent to antibacterial coatings.

(2) Development of FOMULATION technology for high performance adhesive property

  ○ Selection of compounding solution and selection of solvent (the following components are based on weight in total)

TEST
matter One 2 3 4 5 Acrylic resin 100 100 100 100 100 Dispersant 0.1 0.3 0.5 One 1.5 Viscosity (cps) 5,500 5,200 5,150 4,800 4,500 Drying conditions (占 폚 SEC) 100 x 50 100 x 50 100 x 50 100 x 50 100 x 50 SPEED (m / min) 15 15 15 15 15

 - When 1.5PHR of dispersant is added, flowability is good and good.

TEST
matter One 2 3 4 5 Acrylic resin 100 100 100 100 100 Surface modifier 0.1 0.3 0.5 0.7 One Viscosity (cps) 6,700 6,600 6,450 6,200 6,150 Drying conditions (占 폚 SEC) 100 x 50 100 x 50 100 x 50 100 x 50 100 x 50 SPEED (m / min) 15 15 15 15 15

- Good surface smoothness at 1 PHR of surface modifier

TEST
matter One 2 3 4 5 Acrylic resin 100 100 100 100 100 Leveling agent 0.1 0.3 0.5 0.7 One Defoamer 0.5 One 1.5 2 2.5 Viscosity (cps) 5,700 5,600 5,300 5,050 4,800 Drying conditions (占 폚 SEC) 100 x 50 100 x 50 100 x 50 100 x 50 100 x 50 SPEED (m / min) 15 15 15 15 15

- Leveling 0.7PHR / Antifoaming agent 2PHR is judged to be good

(3) Development of coating technology for optimal physical properties

Establishment of coating processing condition according to fabric

- Direct application: When applying directly on fabric, chemicals penetrate into fabric, causing loss of TOUCH feeling of fabric. (It is hard to fabric.) It is difficult to use as product. The change is severe.

- Impregnation coating: Dipping of the resin to be coated on the fabric by coating, this may also cause problems such as transparency and color in the subsequent transfer of DTP. Impregnated fabrics are also hard to use as a product.

- Trancefer-Coating method: The film surface smoothness or DTP process is advantageous for coating, and it is applied to the developed product (refer to FIG. 1).

(TEST by drying temperature)

TEST
matter One 2 3 4 Acrylic resin 100 100 100 100 Dispersant 1.5 1.5 1.5 1.5 Surface modifier One One One One Leveling agent 0.7 0.7 0.7 0.7 Slip agent One One One One Defoamer 2 2 2 2 Antimicrobial agent 0.5 0.5 0.5 0.5 Viscosity (cps) 4,600 4,600 4,600 4,600 Drying conditions (占 폚 SEC) 100 x 50 100 x 80 100 x 100 100 x 120 SPEED (m / min) 18 18 18 18 Mangle Pressure (Kgf / Cm²) 3 3 3 3

(TEST result)

TEST
Properties One 2 3 4 This form △ △ ○ ○ Morphological stability △ △ △ △ Exterior △ △ ○ ○ Stickiness
(Tacky) × (sticky) × (sticky) △ △ Bubble property △ △ △ △

- When tested by drying temperature, 100 ° C × 120 SEC shows good workability and partial improvement due to adhesiveness and air bubbles is required.

(TEST after changing additive)

TEST
matter One 2 3 4 Acrylic resin 100 100 100 100 Dispersant 1.5 2 1.5 2 Surface modifier One One One One Leveling agent One 2 One 2 Slip agent One One One One Defoamer 2.5 2.5 3.5 3.5 Antimicrobial agent 0.5 0.5 0.5 0.5 Viscosity (cps) 4,200 4,000 4,100 3,900 Drying conditions (占 폚 SEC) 100 x 120 100 x 120 100 x 120 100 x 120 SPEED (m / min) 18 18 18 18 Mangle Pressure (Kgf / Cm²) 3 3 3 3

 (TEST result)

TEST
Properties One 2 3 4 This form △ ○ ○ ○ Morphological stability △ ○ △ △ Exterior △ ○ ○ ○ Stickiness
(Tacky) △ ○ X X Bubble property △ ○ △ ○

The condition of No. 2 satisfies the property and the sample work is performed.

Requested 2 samples and 4 samples of TEST for sample work in KATRI.

#2 #4 494 gf / inch 562 gf / inch

As a result of the test, the sticking force is below the target value, and the sticking force is supplemented.

A pre-coating agent is added to give a pretreatment role to acrylic resin.

Primarily treated with pretreatment coating (PU).

TEST
matter One Pretreatment coating resin 100 Viscosity (cps) 6,500 Drying conditions (占 폚 SEC) 100 x 120 SPEED (m / min) 18

After the treatment, the working conditions are set as the above conditions.

(Primary coating + secondary work test result)

TEST
matter One 2 3 4 Primary coating
Pre-treatment resin 100 100 100 100 Secondary coating
Acrylic resin 100 100 100 100 Dispersant 2 2.5 2 2.5 Surface modifier 1.5 1.5 1.5 1.5 Leveling agent 2 2.5 2 2.5 Slip agent 1.5 One One 1.5 Defoamer 2.5 2.5 3.5 3.5 Antimicrobial agent 0.5 0.5 0.5 0.5 Viscosity (cps) 3,900 3,780 3,850 3,600 Drying conditions (占 폚 SEC) 100 x 120 100 x 120 100 x 120 100 x 120 SPEED (m / min) 18 18 18 18 Mangle Pressure (Kgf / Cm²) 3 3 3 3

(TEST result)

TEST
Properties One 2 3 4 This form ○ ○ ○ ○ Morphological stability △ ○ △ ○ Exterior ○ ○ ○ △ Stickiness
(Tacky) ○ ○ ○ ○ Bubble property ○ ○ ○ ○

(4) Coating process on-site process conditions and SCALE-UP sizing

Secondary coating
Acrylic resin 100 Dispersant 2.5 Surface modifier 1.5 Leveling agent 2.5 Slip agent One Defoamer 2.5 Antimicrobial agent 0.5 Viscosity (cps) 3,780 Drying conditions (占 폚 SEC) 100 x 120 SPEED (m / min) 18 Mangle Pressure (Kgf / Cm²) 3

Finally, the present invention is summarized as follows. The coating is divided into a primary coating using PU resin of polyurethane, silicone or acrylic resin and a secondary coating using acrylic resin. The weight of the PU resin and the acrylic resin is coated on the basis of the weight (100) of 2.5% of dispersant, 1.5% of surface modifier, 2.5% of leveling agent, 1% of slip and 0.5% of antibacterial agent.

Drying conditions (℃ x sec) should be 100 x 120, feed rate shall be 18 meters per minute, and the pressure of the mung be 3 kgf / cm².

 (TEST result)

TEST
Properties result This form ○ Morphological stability ○ Exterior ○ Stickiness
(Tacky) ○ Bubble property ○

Due to the above-mentioned sizing ingredients and coating and drying conditions, it has high-performance adhesive properties such as initial adhesion strength of 800 gf / inch or more and re-peelability of 90% or more upon reattaching 10 times. By this technology, So that the product can be developed.

Claims (7)

A printed layer composed of a fiber material and capable of printing an image on one side to form an adhesive surface on the back side of a fabric used as an advertisement, an interior product, and a fancy product,
The coating is divided into a primary coating using a PU resin of one of polyurethane, silicone, and acrylic resin and a secondary coating using an acrylic resin,
As the components included in the primary coating and the secondary coating, the weight of the PU resin and the acrylic resin was 100% by weight based on the weight of the dispersant, PU resin and acrylic resin, respectively, of 2.5% PU resin and an acrylic resin having a weight of 100% based on the weight of the leveling agent, the PU resin and the acrylic resin, which are each 2.5% by weight based on the weight of the surface modifier, the PU resin and the acrylic resin, The antifungal agent, the PU resin and the acrylic resin, each having a weight of 100% by weight, were each coated with a defoamer containing 2.5% by weight of (100)
The drying conditions (° C × sec) are 100 × 120, the conveying speed is 18 meters per minute, the mangle pressure is 3 Kgf / Cm², the initial adhesive strength is 800 gf / inch or more, Peelability,
And a release paper for protecting the pressure-sensitive adhesive layer is added to the pressure-sensitive adhesive layer. delete delete delete delete delete delete

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