KR101248479B1 - Hot melt type urethane adhesives resin composition - Google Patents

Abstract

PURPOSE: A hot melt adhesive resin composition is provided to have excellent adhesive strength, moisture resistance, permeability, and flexibility. CONSTITUTION: A urethane hotmelt adhesive resin composition comprises 20-30 parts by weight of polyol with a number average molecular weight of 400-6000 and 2-3 hydroxy functional groups; 3-10 parts by weight of an organic polyisocyanate; 0.6-4 parts by weight of a chain extender, 50-75 parts by weight of a solvent; 0.1 parts by weight of an antioxidant; 0.5 parts by weight of an adhesive improver; 0.05 parts by weight of a coupling agent; 0.2 parts by weight of a blocking modifier; 0.05 parts by weight of a leveling agent; and 0.1 parts by weight of a yellowing preventer.

Description

Hot melt type urethane adhesives resin composition

The present invention relates to a moisture-permeable urethane hot-melt adhesive resin composition, and more particularly, a highly moisture-permeable urethane used for the production of a moisture-permeable waterproof garment that requires excellent moisture permeability in addition to activity and light weight when worn such as hiking clothes and sportswear. It relates to a hot melt adhesive resin composition.

Climbing clothes, sportswear and the like generally require excellent moisture permeability in addition to activity at the time of wearing, fit, light weight, and the like. Moisture permeability is one of the important characteristics in suppressing the discomfort caused by the moist heat caused by moisture remaining in the body due to sweating or the like in the neck.

As a garment excellent in moisture permeability, the heat-repellent moisture-proof tarpaulin which bonded the film containing a water-swellable moisture-permeable urethane resin and a heat-ray reflective metal micropiece and fiber base cloth using the reactive heat-melting adhesive of a moisture-curable urethane resin is known.

For example, in Japanese Patent Laid-Open No. 2002-370335 (Document 1), the reactive hot melt adhesive does not have moisture permeability in itself. Therefore, when the said adhesive agent is used for adhesion | attachment of a moisture-permeable base material, the adhesive agent seals the moisture-permeable hole which the said moisture-permeable base material has, and as a result, the outstanding moisture permeability which a base material has remarkably decreased.

In addition, since the reactive hot melt adhesive specifically exemplified in Document 1 can form a relatively high hardness adhesive layer, when the adhesive is used for bonding a substrate having flexible mixing, the flexible mixing of the substrate is remarkably. It disappeared and, as a result, may reduce the wearing feeling as clothing.

As mentioned above, the urethane hot-melt adhesive which combines the outstanding state adhesive strength, water-resistant adhesive strength, moisture permeability, and flexibility which does not cause the outstanding moisture permeability and the remarkable fall of the softness of a base material is not known yet.

1. Republic of Korea Patent Publication No. 10-2010-0041692 "Moisture-curable polyurethane hot melt adhesive and laminates and moisture-permeable films using the same" 2. Japanese Patent Laid-Open No. 2002-370335

The present invention has been made to solve the conventional problems, in the present invention to provide a high moisture-permeable urethane hot melt adhesive resin composition that provides excellent moisture-permeability and flexibility while ensuring excellent state adhesive strength, water-resistant adhesive strength as a problem do.

The high moisture-permeable urethane hot melt adhesive resin composition of the present invention, which solves the above problems, uses any one of polyester polyol and polyether polyol alone or mixed, and has a number average molecular weight of 400 to 6000 and a hydroxy functional group per molecule. 20 to 30 parts by weight of 2 to 3 polyols, 3 to 10 parts by weight of organic polyisocyanate, 0.6 to 4 parts by weight of chain extender, 50 to 75 parts by weight of solvent, 0.1 part by weight of heat resistant antioxidant, 0.5 part by weight of adhesion promoter, couple It contains 0.05 parts by weight of ring agent, 0.2 parts by weight of blocker regulator, 0.05 parts by weight of leveling agent and 0.1 parts by weight of anti-yellowing agent, and is mixed so as to have a solid content of 25 to 50%, having a water vapor transmission rate of 1050 to 3600 g / m 2 day,
The polyester polyol may be any one selected from the group consisting of aromatic polybasic acids, phthalic acid, isophthalic acid, terephthalic acid, dicarboxylic acid and aliphatic polybasic acid, succinic acid, adipic acid, and azelaline acid; 200-250 polyhydric alcohol, which is one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1.4 butanediol, 1.3 butanediol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol and heptamethylene glycol Using a high molecular compound obtained by condensation polymerization at
The polyether polyol is any one or more selected from the group consisting of polypropylene glycol, polyethylene glycol, polycaprolactone glycol, polytetramethylene glycol, polycarbonate glycols,
The organic polyisocyanate may be any one or more aromatic isocyanate compounds selected from the group consisting of tolylene diisocyanate, 1.5-naphthylene diisocyanate, and 1.3-phenylene diisocyanate; Any one or more aliphatic isocyanate compounds selected from the group consisting of hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate and xylene diisocyanate; Or any one or more alicyclic isocyanate compounds selected from the group consisting of methylcyclohexane diisocyanate and cyclohexane-1.4-diisocyanate.

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The urethane hot melt adhesive resin composition provided in the present invention may provide excellent moisture permeability and flexibility while ensuring excellent state adhesive strength and water resistant adhesive strength when used in garment manufacturing such as mountain climbing clothes and sportswear.

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

The present invention relates to a highly moisture-permeable urethane hot melt adhesive resin composition used in the production of a moisture-permeable waterproof garment that requires excellent moisture permeability in addition to the activity and lightness when worn such as mountaineering clothes, sportswear, etc., the high moisture-permeable urethane hot melt according to the present invention The adhesive resin composition includes 20 to 30 parts by weight of a polyol obtained by singly or mixing a polyester polyol having a number average molecular weight of 400 to 6000 or a polyether polyol, 3 to 10 parts by weight of an organic polyisocyanate, 0.6 to 4 parts by weight of a chain extender, and a solvent. 50 to 75 parts by weight, heat-resistant antioxidant 0.1 parts by weight, adhesion promoter 0.5 parts by weight, coupling agent 0.05 parts by weight, blockkin regulator 0.2 parts by weight, leveling agent 0.05 parts by weight and yellowing agent 0.1 parts by weight, the solid content It is made by mixing to 25 to 50%.

The polyol is a major component for imparting adhesiveness and moisture permeability to an adhesive, and the polyol is obtained by condensation of a known polybasic acid and a polyhydric alcohol, and can be broadly classified into a polyester polyol and a polyether polyol. The polyester polyol may be prepared and used, and polyether polyols may be used by introducing a commercialized product.

That is, the said polyol which comprises this invention uses polyester polyol or polyether polyol obtained by the polycondensation reaction of polybasic acid and a polyhydric alcohol.

Here, polybasic acids that may be used in the preparation of the lollyester polyols include phthalic acid, isophthalic acid, terephthalic acid, dicarboxylic acid as aromatic polybasic acids, and are prepared using aliphatic succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. can do.

In addition, polyhydric alcohols that may be used in the production of polyester polyols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1.4 butanediol, 1.3 butanediol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, and the like. Can be used. By polycondensation of the polybasic acid and polyhydric alcohol at 200-250 ℃ can be prepared the polyester polyol.

According to the present invention, the polyether polyol may be any one or more selected from the group consisting of polypropylene glycol, polyethylene glycol, polycaprolactone glycol, polytetramethylene glycol, and polycarbonate glycols.

These polyols are those having three or less hydroxy functional groups per polyol molecule, and are preferably mainly two.

According to the present invention, it is preferable to use a polyol having a number average molecular weight of 400 to 6000, more preferably a polyol having a molecular weight between 1000 and 4000 can be mainly used, and a copolymer of these polyols or a mixture thereof It may also be formulated.

According to the present invention, an organic polyisocyanate which is an isocyanate compound constituting the resin composition is for addition reaction to a polyol, and a known aromatic isocyanate compound, an aliphatic or alicyclic isocyanate compound can be used.

The aliphatic isocyanate compound may be any one or more selected from the group consisting of hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, xylene diisocyanate, and the alicyclic isocyanate isophorone diisocyanate, methylcycloisocyanate. Hexane diisocyanate, cyclohexane-1.4- diisocyanate may be any one or more selected from the group consisting of. As the aromatic isocyanate, any one or more selected from the group consisting of tolylene diisocyanate, 1.5-naphthylene diisocyanate, 4.4-diphenylmethane diisocyanate and 1.3-phenylene diisocyanate can be used.

According to the present invention, the solvent constituting the resin composition is acetone, methyl ethyl ketone, mail isobutyl ketone, toluene, xylene, ethyl acetate, n-butyl acetate, cellosolbu acetate, isopropyl alcohol, dimethylformamide, n Any one selected from the group consisting of -methyl-2-pyrrolidone, tetrahydrofuran and cyclohexanone is used.

According to the present invention, the resin composition is further added to any one or more selected from the group consisting of antioxidants, heat stabilizers, adhesion promoters, polymer additives, coupling agents, blocking agents, leveling agents, organic and inorganic additives, yellowing agents can do.

When synthesizing a highly moisture-permeable hot melt adhesive as the polyol and isocyanate of the present invention described above, a polyol having a polyester polyol molecular weight range of 1000-4000 is used alone or in combination, polyethylene glycol molecular weight 1500-6000 for moisture permeation function It synthesize | combines using the polyol of the range together. In addition, polytetramethylene glycol, polycaprolactone polyol, and polycarbonate polyol may be introduced and used in combination to control physical properties, and synthesis is performed through addition reaction between these polyols and isocyanates. It is more preferable to use 4.4-diphenylmethane diisoyanate as the furnace.

In addition, by forming a hard segment by adding a chain extender to enhance the formation and physical properties of the adhesive coating film, the chain extender used at this time can be used 1.4 butanediol, 1.6- hexanediol, neopentyl glycol, trimethylol propane It can also be used as a composite.

In addition, it is an antioxidant, heat stabilizer, tackyfier and polymer additive for improving adhesion. It is a polyamide or polyester resin, a coupling agent, an additive to control blocking property, a leveling agent, various organic and inorganic additives, and yellowing by UV. Silanes (e.g., methacrylsilane) can be added as a yellowing inhibitor or coupling agent, and a solvent is used for smooth liquid maintenance when the molecular weight is increased by the synthesis reaction before and after the temperature of 60-100 ° C. Dilute by diluting the solid content in 25-50% range.

At this time, the leveling agent or coupling agent is preferably used to include 0.1 parts by weight based on the total weight of the mixture.

In addition, the total amount of additives such as a leveling agent, a coupling agent, a heat resistant antioxidant, and a yellowing inhibitor may be added so as to include 1 part by weight or less.

In addition, it is preferable to use the polymer additives, adhesion promoters, blocking regulators and the like to use the amount of 1 to 8 parts by weight.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, the present invention is not limited to the following examples, and any modifications can be made within the scope of the present invention.

[Example]

1. Highly moisture-permeable urethane hot melt adhesive

Using a polyol having a number average molecular weight of 400 to 6000, a highly moisture-permeable urethane hot melt adhesive resin composition was prepared in a composition ratio as shown in Table 1 below, and a hot melt adhesive was prepared by the process described below.

[Hot Melt Adhesive Manufacturing Process]

a. The polyol is prepared by removing and melting moisture by storing at least 100 hours at a temperature of 100 ℃ or more.

b. A polyol, a chain extender, a heat resistant antioxidant, and a solvent are added, followed by stirring.

c. The reaction is started by adding isocyanate at a temperature in the range of 50-65 ° C., and the temperature is increased. The reaction is carried out before and after 4 hours at 70-80 ° C. for aromatic isocyanate and 4 hours at 85-100 ° C. for aliphatic or alicyclic isocyanate. React back and forth.

d. After the isocyanate reaction is completed, the additive and the solvent are added to each other, followed by stirring to terminate the synthesis.

The unit of the mixing ratio of each mixture of following Table 1 is a weight ratio.

division Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Example
8 Solvent 65 65 65 65 65 65 65 65 Polyol A 28 - 14 - 14 14 14 14 Polyol B - 28 14 14 14 14 14 14 Polyol C - - - 14 - - - - Aromatic isocyanate compounds 4 4 4 4 - - 4 4 Aliphatic Isocyanate Compounds - - - - 4 - - - Alicyclic isocyanate compounds - - - - - 4 - - Chain Extender A 2 2 2 2 2 2 - - Chain Extension B - - - - - - 2 - Thermal Antioxidant 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Adhesion Promoter 0.5 0.5 0.5 0.5 0.5 0.5 0.5 4.5 Coupling agent 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Blocking regulator 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Leveling agent 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Yellowing inhibitor 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Solid content 35% 35% 35% 35% 35% 35% 35% 39%

Note) 1. Solvent: Methyl ethyl ketone, dimethylformamide, ethyl acetate

2. Polyol A: A polyester polyol having a number average molecular weight of 4,000 (B-4000H (marker): 1.6HD-adipate) was used.

3. Polyol B: polyether polyol having a number average molecular weight of 2,000 (SK-45T (marker: KPX green chemical): polyethylene glycol)

4. Polyol C: polyether polyol having a number average molecular weight of 2,000 (N-980R (marker: Nippon Polyurethane (NPU)): polycarbonate diol)

5. Aromatic isocyanate compound: Cosmonate-PH (Kumho Mitsui Chemicals), 4.4 diphenylmethane diisocyanate (MDI) is used

6. Aliphatic isocyanate compounds: Desmoder H (marker: Bayer), hexamethylene diisocyanate (HDI) is used

7. Cycloaliphatic isocyanate compounds: Basonat I (marker: BASF) and isophorone diisocyanate (IPDT)

8. Chain extender A: 1,4BD (marker: SK), 1,4 butanediol is used

9. Chain extender B: EG (Imaker: SK), ethylene glycol is used

10. Heat resistant antioxidant: Use Songnox-2450 (marker: Songwon Industry)

    SN-1010, SN-1076 also available

11. Adhesion Promoter: Regalite R1100 (marker: EASTMAN chemical, Hydrocarbon resin)

12 coupling agent: OFS-6030 (marker: Xiameter), using methacrylosilane

13 Blocking regulator: Elvacite 2013 (marker: Lucite international), thermoplastic acrylic resin

14 Leveling agent: Use BYK-325 (marker: BYK)

15 Yellowing inhibitor: Lowilite 35 (marker: chemtura), bentotriazole-based UV stabilizer

[Comparative Examples 1 and 2]

Purmelt R-508B (marker: Henkel) was prepared using a known hot melt adhesive, prepared by melting with a solid content of 30% using solvent-MEK and DMF (Comparative Example 1), and Desmomelt 540/1 (marker: Bayer) was prepared. Prepared and melted to a solid content of 30% by using a solvent MEK, DMF (Comparative Example 2) was compared and tested.

2. Evaluation of high moisture permeability urethane hot melt adhesive

The adhesive strength and moisture permeability of the hot melt adhesives of Examples 1 to 8 and Comparative Examples 1 and 2 were compared and evaluated, and the results are shown in Table 2 below.

Ingredient Example Comparative example One 2 3 4 5 6 7 8 One 2 Adhesion strength (before / after washing) (kgf) 5.1 / 3.9 5.1 / 3.3 5.4 / 3.8 5.4 / 4.1 5.7 / 3.4 5.9 / 3.5 5.9 / 4.0 5.6 / 3.7 4.9 / 2.9 5.0 / 3.5 Moisture permeability
(g / ㎡day) 1050 3600 1940 1760 2060 1900 2100 1050 100 120

Note) 1. Adhesion strength: Measured by universal testing machine after 60 hours at 60% humidity for 40 hours.

2. Moisture permeability: test method of moisture vapor cup. Measuring fabric is made of polyester by coating adhesive on TPU film after waterproof coating.

* Set the water vapor permeability target: 1500 or more, and test the adhesive strength: 3kg or more.

As can be seen from the results of the above [Table 2], the adhesive strength and moisture permeability of the hot melt adhesives of Examples 1 to 8 and Comparative Examples 1 and 2 prepared according to the present invention were tested. 8 to 8 was confirmed that the excellent performance of both the adhesive strength and the moisture permeability compared to Comparative Examples 1 and 2.

In addition, in the hot melt adhesive of Examples 1 to 8, in the case of moisture permeability, it was found that the higher the content of polyol B, the better the moisture permeability, and to prevent deterioration of water resistance and mechanical properties that become weak as the amount of polyol B is increased. It was found that the adhesion strength can be improved by appropriately mixing polyols A, C and polyol B.

As described above, the highly moisture-permeable urethane hot-melt adhesive resin composition according to the present invention has been described with reference to preferred embodiments, and the superiority thereof has been confirmed. It is to be understood that various modifications and changes can be made in the present invention without departing from the scope thereof.

Claims (6)

Any one of polyester polyols and polyether polyols is used alone or mixed, 20-30 parts by weight of a polyol having a number average molecular weight of 400 to 6000 and 2 to 3 hydroxy functional groups per molecule, and an organic polyisocyanate 3 to 10 Parts by weight, chain extender 0.6-4 parts by weight, solvent 50-75 parts by weight, heat-resistant antioxidant 0.1 parts by weight, adhesion promoter 0.5 part by weight, coupling agent 0.05 parts by weight, blockkin regulator 0.2 parts by weight, leveling agent 0.05 parts by weight And containing 0.1 parts by weight of anti-yellowing agent, to be mixed so as to have a solid content of 25 to 50%, having a water vapor transmission rate of 1050 ~ 3600g / ㎡day,
The polyester polyol is any one selected from the group consisting of aromatic polybasic acids, phthalic acid, isophthalic acid, terephthalic acid, dicarboxylic acid and aliphatic polybasic acid, succinic acid, adipic acid, azelaic acid and sebacic acid; 200-250 polyhydric alcohol, which is one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1.4 butanediol, 1.3 butanediol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol and heptamethylene glycol Using a high molecular compound obtained by condensation polymerization at
The polyether polyol is any one or more selected from the group consisting of polypropylene glycol, polyethylene glycol, polycaprolactone glycol, polytetramethylene glycol, polycarbonate glycols,
The organic polyisocyanate may be any one or more aromatic isocyanate compounds selected from the group consisting of tolylene diisocyanate, 1.5-naphthylene diisocyanate, and 1.3-phenylene diisocyanate; Any one or more aliphatic isocyanate compounds selected from the group consisting of hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate and xylene diisocyanate; Or methylcyclohexanediisocyanate, cyclohexane-1.4-diisocyanate, and any one or more alicyclic isocyanate compounds selected from the group consisting of a highly moisture-permeable urethane hot melt adhesive resin composition. delete delete delete delete delete