JPS5842675A - Water-based polyester hot-melt adhesive - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which contains a polyester resin prepared by using a specified amount of an aromatic dicarboxylic acid contg. a sulfonic acid metal salt group as polycarboxylic acid component, has excellent resistance to water and solvent and adhesiveness and is useful for bonding textile material, metal, paper, etc. CONSTITUTION:A polyester resin is prepared by interaction of (a) a dicarboxylic acid component consisting of (1) 0.5-20mol% aromatic dicarboxylic acid contg. a sulfonic acid metal salt group (e.g., sodium sulfoterephthalate) and (2) 99.5- 80mol% aromatic or aliphatic dicarboxylic acid not containing any sulfonic acid metal salt group and (b) a polyol component (e.g., 2-8C aliphatic glycol). The aqueous hot-melt adhesive is prepared by blending (A) said polyester resin, (B) a water-soluble organic compd. with a b.p. of 60-200 deg.C (e.g., n-butylcellosolve), (C) water and (D) powdered thermoplastic resin with a particle diameter of 200mu or smaller in the blend ratio satisfying the equationsI-IV.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous polyester hot melt adhesive, and more particularly to an aqueous polyester hot melt adhesive having excellent water resistance, solvent resistance and adhesive properties.

Traditionally, hot melt adhesives have been used in film, powder, pellet, and paste forms to bond textiles, nonwoven fabrics, films, metals, etc., and will continue to grow due to their ease of handling and excellent adhesive strength. is expected. Thermoplastic resins that are currently preferred include ethylene/vinyl acetate copolymers, polyamide resins, and copolymerized polyester resins.

However, each of these thermoplastic resins has some drawbacks. That is, ethylene/vinyl acetate copolymers have insufficient bath agent resistance and heat resistance, and l-lyamide resins have excellent solvent resistance but poor water resistance. -10,000W polyester resin has very excellent properties such as solvent resistance, water resistance, heat resistance, and adhesiveness, and is highly evaluated as a resin with the best balance of each performance. However, when these ester resins having excellent performance are used as an aqueous paste, there are disadvantages in terms of performance. That is, when dispersing maryester resin powder in water, it is necessary to use a water-soluble resin such as polyethylene oxide or carbomethyl cellulose or a surfactant, which results in a decrease in water resistance, adhesiveness, etc. Therefore, the current situation is that there is a strong desire to develop a technology for making maryester resins water-based without impairing the above-mentioned excellent performance.

Therefore, the present inventors have conducted various intensive studies on water-based preester hot melt adhesives having excellent water resistance, adhesion, solvent resistance, and heat resistance, and as a result, have arrived at the present invention.

That is, the present invention provides 0.6 to BO mole of (A) * recarboxylic acid component.
is a sulfonic acid metal group-containing aromatic dicarboxylic acid, a polyester resin having a molecular weight s, ooo #so, ooo,
@Contains a water-bathable organic compound with a boiling point of 60 to 200°C, (C) water, and (D) thermoplastic resin powder with a particle size of 80°C or less,
and (4), (9), (C), and (D) satisfy the following conditions 2), I), 1, and 4).

Formula 1) (4)+(B)+(0)+(D)” Woo
(Weight ratio) 2t! 1(A)+(n)/(n)+(c)
-s ~to7ms-s.

(weight ratio) formula powder (D)/(4)+(D)=O~o, sa (weight ratio) formula 4) @/CB)+((ri=O~o, gg' (weight ratio) book In the present invention, by using an aqueous polyester resin mainly composed of a sulfonic acid metal base-containing polyester resin (4), an aqueous polyester hot melt adhesive having excellent water resistance, adhesiveness, solvent resistance, and heat resistance can be obtained.

◇Specifically, the polycarboxylic acid component is an aromatic dicarboxylic acid containing no sulfonic acid metal base! 40 to 99.5% roux, aliphatic or alicyclic dicarboxylic acid as, ao mol, and sulfonic acid metal base-containing aromatic dicarboxylic acid 0.5 to 20 mol, and the polyol component has 8 to 8 carbon atoms. It is preferable that the polyester resin is made of aliphatic glycol of a and/or alicyclic glycol having 6 to 1 carbon atoms.

Examples of aromatic dicarboxylic acids that do not contain a sulfonic acid metal group include terephthalic acid, isophthalic acid, orthophthalic acid, g,6-7tale dicarboxylic acid, and the like. These aromatic dicarboxylic acids that do not contain sulfonic acid metal groups contain 40 to 99% of the bricarboxylic acid component.
．． Preferably it is 5 mol%. If it is less than 400 mol%, the mechanical strength and water resistance of the polyester resin will be poor, which is not preferable. If it exceeds 99.8 mol%, the polyester resin will not be dispersed in the system.

Aliphatic or alicyclic dicarboxylic acids include, for example, cohetaic acid, adipic acid, azelaic acid, cepacic acid, dodecanedioic acid, dimer acid, tesirahedoidal phthalic acid, hexaoctaic acid 1:+7 talic acid, Examples include Heyd's capsule inhetathalic acid, hexane gastric terephthalate, and the like. The aliphatic or alicyclic dicarboxylic acid is preferably 59.5 to 0-1-Rh of the polycarboxylic acid component.

If it exceeds 59.5 mol%, water resistance and coating film strength will decrease and tackiness will appear.

Additionally, arhydroxybenzoic acid, cy(1- and dorogyetoxy)benzoic acid or human tetraxypivalic acid,
r-Buty-a-lactone, ξ-butyric acid, etc. can be used if necessary. ◎ Also, if necessary, polycarboxylic acid having five or more functional groups such as trimellitic acid and bi-tetramellitic acid can be completely added to the carboxyl # component. It can be used as long as it is less than 6 mole attack.

Examples of aliphatic glycols having carbon number S-a include ethylene glycol, propylene glycol, 1. II.Pudapanediol, l,4-butanediol, neopentyl glycol, 1. IS-bentanediol, diethylene glycol, 1,6-hequinanediol and the like can be mentioned. As an alicyclic glycol having 6 to 1 carbon atoms, 1,4
- Shita-tetrahexane dimetatool, etc. can be mentioned.

Aliphatic glycols having 2 to 8 carbon atoms and/or fatty glycols having 6 to 11 carbon atoms are present in an amount of 98 to 100 mol based on the total lyol component. Trifunctional or higher functional polyols such as ruethane, daliliol, pentaerythritol, etc. can be used as long as the total meliol content is less than 10%. Furthermore, l realkylene glycols having a molecular weight of vooo or less, preferably 6000 or less, such as i
If necessary, add f & lyethylene glycol, melip-tetrabirendaricol, or detramethylene glycol to 16 parts by weight or less, preferably 1 ol per total lyol component.
Examples of aromatic dicarboxylic acids containing sulfone metal bases include sulfoterephthalic acid, .-sulfoisophthalic acid, sulfothalic acid, sulfonaphthalene, ? -Dicarboxylic acid,! Metal salts such as l-(sulfophenoquine) cypress 7-talic acid can be mentioned.As metal salts, TJ
L e M & * K # M g e O &#
Ou.

Examples include salts such as 1., and *a and Preferably O0a to 107 ru.1. Even better l,
O-7 is complete. If the amount is less than 90 mol, the preester resin will not be dispersed in water at all, and if it exceeds 90 mol, the resulting film will have very poor water resistance.

The molecular weight of the ester resin according to the present invention is s, oo.

~so,ooo, preferably s,ooo~as,ooo
It is. If the molecular weight is less than 3,000, the adhesive strength will be poor, and if it exceeds go, ooo', the dispersibility in water will be poor, which is not preferred.

The ester mWI of the present invention can be produced by conventional methods.

The ester resin used in the invention may be either crystalline or non-crystalline, or may be a mixture thereof. Particularly preferred is a mixture of amorphous ester resin=crystalline ester resin-5-30+Ii~)0 (weight ratio).

The water-soluble organic compound (-) with a boiling point of 60 to 100°C used in the present invention has a solubility in 1 ton of water at go°C of J! An organic compound of OP or higher, which does not contain any heteroatoms other than oxygen, is preferably an eyelid. Specific examples include aliphatic and alicyclic alcohols, ethers, esters, and ketone compounds. 0 More specifically, for example, methanol, ethanol, l-prepanol, 1-prepanol, n-butanol, 1-
Rice alcohols such as butanol, 11-butanol, t@rt-butanol, glycols such as ethylene puripur and tetrapyrene glycol, methyl 74solp,
Ethilse Stomach Solp, Isopta Birse Stomach Solp, t@rt
- Puricol derivatives such as Putilse Gastric Solv, - Putil Setanlup, 3-methyl-3-methoxybutanol, n-butyl-kW Solp Acetate, dioxane, Ni such as Tetotsuheide 07ran, ethyl acetate, etc. esters, methyl ethyl ketone,
Vlp w otatano? , Schiff's decanone, and ketones such as Jitter's non. Particularly preferred are n-butylcetinol, ethylcetinol, isopropanol, and the like. These water-soluble organic compounds can be used alone or in combination. The boiling point of these water-soluble organic compounds is necessarily in the range of 60 to 200°C. If the boiling point reaches 60℃ and there is none, mix preester resin with this organic compound! Fast drying is not achieved after application of low-temperature hotmelt adhesives, which are difficult to reach at high enough temperatures to melt.

Furthermore, when an amide or sulfonic acid ester compound is used as a water-based compound, the drying properties are poor, and at the same time, the storage tube chemotaxis of the water-based ester, hot melt, adhesive, and agent becomes poor. .

Thermo-Machida Resin Powder (D) of the Present Invention qt A pulverized product of a thermo-Machida resin such as a conventional giri ester resin, polyethylene/vinyl acetate, Melier or Stell resin (4) of the present invention, and a liester resin is preferred. , .

As this crystalline polyester resin, crystalline Bossester W resin and/or the crystalline polyester resin (A) of the present invention in which sulfonic acid metal base-containing aromatic dicarboxylic acid is not copolymerized are preferable, and in particular, the crystalline polyester resin (A) of the present invention is preferably It is preferable that the crystalline ester resin has a realkylene glycol component of 18% by weight (paired glutamic acid) of y000 or less. Furthermore, the particle size of the thermoplastic resin powder is 800. μ or less, preferably ・10
．． If the O particle size is less than 0 μ and exceeds 200 μ, a smooth and uniform film may not be obtained when applying the resulting aqueous polyester hot melt adhesive, or if a rotary screen is used. A water-based ester resin can be obtained by blending an Olly ester resin (1) which causes problems such as clumping, water (0) and, if necessary, a more water-soluble organic compound (@). One of the aqueous ester hot melt adhesives of the present invention is produced by stirring and mixing a previously prepared aqueous polyester resin and thermoplastic resin powder. On the other hand, for example, the water-based polyester resin contains (A) &reester resin and @) a water-bathable organic compound at 50~J! Mix in advance at 00℃ and add (0) water or (
It is produced by a method such as adding a mixture of A) and (2) to water and stirring at 40 to 120°C. When mixing the thermoplastic resin powder with the aqueous preester resin, water may be added if necessary.

In these methods, (4) polyester resin, (9)
The blending ratio of the water-soluble organic compound, (C) water, and (D) thermoplastic resin powder is an important factor in maintaining the performance of the water-based ester hot melt adhesive, and is expressed by formula 1),! )
, I and the ship's compounding ratio (weight ratio).

Formula 1) (A) + (9) + (0) + (D) Proverb 100
Formula '(A)+(D)/(B)+(Q)=6~?
On98-30 age (D) / (A) + (D)
= o ~ 0.98 formula 4) (B) / CB) + ((ri = O ~ 0.66 (4) ester resin and (D) thermoplastic resin powder contained in the aqueous ester hot melt adhesive .If the weight is not 11lL or exceeds 70%, use water-based ``Meryester Hot Mel F''.
Adhesive viscosity is low! The growth rate is too high, which is not desirable.

゛ (2) Thermoplastic resin powder contained in the tomelt adhesive is (A) Resin and (D) Thermoplastic resin powder. 5 pairs of sum. , 98, the aqueous Merry ester will no longer be uniformly dispersed in the resin.

Contained in water-based ester hot melt adhesives (mouth)
If the amount of the water-soluble organic compound exceeds 0.66 relative to the sum of (C) water and (B) water-bathable organic compound, the drying properties will decrease, which is undesirable. This water-based polyester hot melt adhesive, which can be made into amino resin, engineered mexi resin, isocyanate, is used for fabrics,
It exhibits unprecedented water resistance, solvent resistance, heat resistance, and adhesive properties as an adhesive for textile products such as non-woven fabrics, steel plates, metals such as neem plates, paper, and plastic ivy film. be. The water-based/&reester netmel F adhesive of the present invention may optionally contain a water-soluble resin,
Thickeners such as amines, pigments, dyes, and various additives can be added.

Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples.In the examples, "parts" simply indicate parts by weight.

The characteristics of the species ★ were evaluated using a molecular weight measuring device (Model 11, manufactured by Hitachi Seisakusho) according to the following method.

Temperature increase rate 1 by crystal display - scanning calorific value needle (manufactured by Shimadzu Corporation)
Measurement was performed at 0°C/min.゛Powder softening point fully automatic melting point measuring device (MI?'l'LmR company, MOD
]ILFF-1).

Particle size of initial aqueous dispersion Measured using a grindmeter and an optical microscope.

(trans)adhesion Compliant with J Engineering 8 and ■14.

-Water resistance Based on Ixa L 104g, measured by peel strength retention after washing three times.

η Measured by peel strength retention of bales that were dry-cleaned three times at 10°C using solvent-resistant parked roethylene.

Production example L 430 parts of dimethyltereate, 466 parts of dimethyl isophthalate, 4.1 parts of dimethyl 6-sodium sulfoisophthalate, 448 parts of ethylene glycol, neopentyl glycol aoog, 0.44 parts of lead acetate, sodium acetate^O , OS part, and 0.48 parts of antimony trioxide were placed in a reaction vessel, and a transesterification reaction was carried out at 160° C. to 10° C. over a period of 1 hour. Next, the pressure inside the reaction system was gradually reduced while raising the temperature at R60°C, and after 1 hour, 6-
and finally 860℃, O01~0.3ms
) Polycondensation reaction of Ig was carried out under reduced pressure for 1 hour, and the molecular weight
.

A non-quality glyceryl ester resin (B-1) having a temperature of 'F, 000 and a softening point of 162°C was obtained. As a result of compositional analysis such as NMR, the composition of the polyester resin (B-1) was found to be tereyak acid 4s.
mol -, isophthal 116 mol, 5-sodium sulfoisophthal s 3 mol, -, ethylene glycol 82
mol, and 48 mol of neopentyl glycol.

Furthermore, crystalline ester tree 1 was prepared in exactly the same manner except that the raw materials shown in Table 1 were used. (A-1) ~ (Mu-5),
Amorphous meliester trees m<'5-a) to (!l-4) were obtained. Their characteristic values were as shown in Table 1-1 and Ichibata.

, the following is a blank space 1 Table-1 Example L 4 parts of polyester resin (*-1) gasL'*lyester resin (ml-1) and 10 parts of n-butylce gastrosol were melt-mixed at 130°C, and then this 6 ounces of water to the molten mixture
By adding 0 part with stirring, a blue-white particle size of 1μ is obtained.
The following stable aqueous l-lyester resin (0-1) was obtained.

Next, when 100 parts of the obtained aqueous resin (0-1) and 30 parts of powder of crystalline polyester resin (I) having a particle size of 100μ or less were mixed with stirring, the aqueous l-lyester was uniformly dispersed. Hot melt adhesive (D-1) was obtained.

The true ester hot melt obtained in this way)
Using a rotary screen, apply adhesive (D-1) to preed of preester/cotton (SA/38) with a basis weight of 1.
5f/d, and then dried at 110°C for S minutes, and then coated with the untreated board at 150°C for 0.
Adhesion was carried out for 10 seconds under the condition of 5%.

The peel strength of the resulting adhesive bleed was 6 B Of/1n.
oh, and the peel strength retention rate after washing test and dry cleaning test was 95 and 9o-, and it was found that it had excellent adhesion, water resistance, and solvent resistance.

Examples 2 to 6 Comparative Examples 1 to 6 Aqueous polyester resins (〇-2) to (0-
After obtaining 5), water-based polyester hot melt adhesives (D-ffi) to (D-6) shown in Table 3 were obtained.

Table 4 shows the properties and performance of the resulting aqueous 1-reester hot melt adhesive.

For comparison, water-based polyester resin (0
, 6) to (c, e) were obtained. Water-based ester resin (a
-s) and (o-s), stable dispersions were not obtained. Next, aqueous L-ester net melt l' adhesive (D
-7) to (D-10) 6 The performance of the obtained aqueous preester hot melt adhesives is shown in all
3 Table (book) (1)
ooO) W a O / 1m / 311 // 3
'F, Is/@J! / O, Is (4k
Ratio) Maximum particle size (l OO#, melting point λl) °C (Gengiri ester resin powder TEM/TE PA/AA/IG/BD=) O/10/Lazy 0
/40/go (mole ratio) Maximum particle size <100μ, melting point zs*℃ (4) Meliamide resin powder QR engineering L-t@x IF (
1M81RvExaxx AG) Maximum particle size <200μ, crystal melting point 115°C Abbreviations indicate the following.

TPAI terephthalic acid 1tl ethylene glycol EP
M: Iso-7-talic acid BD Nibutanediol AA, Adipic acid P-T Mθ: Bo'1l-r) Ramethine glycol and the following margins

Claims (1)

[Claims] (A) & 01Is to 20 mol of the recarboxylic acid component,
A polyester resin JB with a molecular weight of s, ooo -so, ooo whose exterior is an aromatic dicarboxylic acid containing a sulfonic acid metal group, a water-soluble organic compound with one point at go-goo°C, (C) water, (p) particle size 200μ Contains the following thermoplastic resin powder, and (4), (to)), (C) and (D)
A water-based polyester hot melt adhesive characterized by satisfying the following formula: win, comb, ship. 21) (4) + (6) + (c) + (D) -z o o
(Weight ratio) formula ■ (4) + (yu/ (B) + (
(Ritomi 5~70795~go (weight ratio) formula (transformation) (D)
/(4)+(D)-0~o, *a (weight ratio) Formula 4
) (B)/(B) + (c) -o~00-6
(weight ratio)