CN115141578A - Single-component water-based spray adhesive - Google Patents

Abstract

The invention relates to a single-component water-based spray adhesive, application thereof and a product containing the single-component water-based spray adhesive. The single-component water-based spray adhesive comprises a water-based neoprene dispersion, wherein the increase of the Shore A hardness of a formed adhesive film in 0-10 hours accounts for more than 90% of the increase of the Shore A hardness of the formed adhesive film in 0-1000 hours; a styrene-acrylate copolymer dispersion having an amount of solid components of 15 wt% to 25 wt%, relative to the total weight of the solid components of the aqueous neoprene dispersion; a polyol ester free of hydroxyl groups in an amount of 0.9 wt% to 3.8 wt%, relative to the total weight of the aqueous spray glue; an amino acid in an amount of 4 wt% to 15 wt%, relative to the total weight of the aqueous neoprene dispersion; and optionally a nano-metal oxide and an adjuvant. The spray glue of the invention has short initial adhesion time, long open time and good room temperature storage stability.

Description

Single-component water-based spray adhesive

Technical Field

The invention relates to a single-component water-based spray adhesive, application thereof and a product containing the single-component water-based spray adhesive.

Background

The spray glue used for bonding between the sponge and the sponge or other base materials in the fields of soft furniture, rail transit and the like mainly comprises a solvent type styrene-butadiene-styrene block copolymer adhesive (hereinafter referred to as solvent type SBS adhesive), a solvent type chloroprene adhesive, a polyolefin hot melt adhesive and a water-based chloroprene adhesive.

The initial adhesion of the solvent type SBS adhesive and the solvent type chloroprene adhesive is very quick, but the used solvents are benzene, ketone, chlorinated solvent and the like, and the solvents are heavy in smell, not beneficial to the bodies of workers, cause environmental pollution and have potential safety hazards. In addition, the solvent-type SBS binder has the defects of short open time, poor heat resistance, easy yellowing, easy pulverization and the like.

The polyolefin hot melt adhesive has the advantages of environmental protection and short open time. The polyolefin hot melt adhesive is easy to rebound for bonding between sponges with higher thickness and larger rebound force, and has a wetting and adhering effect on the base materials such as the sponges which is not as good as that of a solvent-type SBS adhesive and water-based neoprene adhesive.

The water-based neoprene adhesive comprises single-component water-based neoprene adhesive and double-component water-based neoprene adhesive. The initial adhesion effect of the bi-component waterborne neoprene adhesive can be comparable with that of a solvent-based SBS adhesive, but the initial adhesion effect is short in opening time, the requirement on the precision of glue spraying equipment is high, the requirement on the proportion of the two components is strict, and the operation requirement on field workers is high. In addition, the investment cost of glue spraying equipment of the bi-component waterborne chloroprene rubber adhesive is high, and the component B is easy to block the glue spraying equipment, so that the popularization and the use of the bi-component waterborne chloroprene rubber adhesive are greatly limited. The single-component water-based neoprene adhesive is simple to operate, but has insufficient initial adhesion.

In order to improve the initial adhesion of the single-component water-based neoprene adhesive, a plasticizer can be added into the adhesive. For example, phthalate and aliphatic dibasic acid ester plasticizers are used in one-component waterborne neoprene adhesives to improve tack. JP2000219859A2 mentions the use of dibutyl phthalate (DBP) and butyl sebacate (DBS), JP2004197028A2 mentions the use of dibutyl phthalate (DBP), WO0134718C2 mentions the use of diisobutyl phthalate (DIBP), US9023948B2 mentions the use of plasticizers such as dialkyl phthalates, dialkyl adipates and dialkyl sebacates for use in aqueous neoprene, which have problems in terms of safety, environmental protection or degradability, and also have poor solubility and dispersibility in aqueous neoprene, and problems such as phase separation, skinning, generation of particles and gels tend to occur in aqueous neoprene which has a relatively high crystallization rate.

Therefore, the industry is in need of developing a one-component water-based neoprene adhesive which has strong initial adhesion, is stable in storage and has excellent spraying property.

Disclosure of Invention

The invention aims to provide a single-component water-based spray adhesive, application thereof and a product containing the single-component water-based spray adhesive.

The one-component aqueous spray glue according to the invention comprises the following components:

a. the shore A hardness increment of an adhesive film formed by the aqueous neoprene dispersion in 0 hour to 10 hours accounts for more than 90% of the shore A hardness increment of the adhesive film formed by the waterborne neoprene dispersion in 0 hour to 1000 hours;

b. a styrene-acrylate copolymer dispersion having an amount of solid components of 15 wt% to 25 wt%, relative to the total weight of the solid components of the aqueous neoprene dispersion;

c. a polyol ester free of hydroxyl groups in an amount of 0.9% to 3.8% by weight relative to the total weight of the aqueous spray;

d. an amino acid in an amount of 4 wt% to 15 wt%, relative to the total weight of the aqueous neoprene dispersion;

e. optionally a nano-metal oxide; and

f. optionally an auxiliary agent.

According to one aspect of the invention, there is provided the use of the one-component water-based spray glue provided according to the invention for the preparation of a bonded product.

According to a further aspect of the invention, there is provided the use of the one-component water-based spray glue provided according to the invention for bonding sponges.

According to a further aspect of the invention, there is provided a product comprising a one-component aqueous spray-bonded or sealed substrate provided according to the invention.

According to still another aspect of the present invention, there is provided a bonding method comprising the steps of:

I. applying the one-component aqueous spray according to the invention to at least one surface of a substrate; and

contacting the substrate surface treated in step I with the substrate itself or a surface of an additional substrate.

According to a further aspect of the present invention there is provided a bonded product made according to the bonding method provided by the present invention.

According to a further aspect of the present invention, there is provided a product comprising a substrate and a coating layer formed by applying the one-component waterborne spray provided according to the present invention to the substrate and curing the applied one-component waterborne spray.

According to a further aspect of the present invention, there is provided a process for preparing a one-component aqueous spray glue provided according to the present invention, comprising the steps of: the component a) an aqueous chloroprene dispersion, the component b) a styrene-acrylate copolymer dispersion, the component c) a polyol ester containing no hydroxyl groups, the component d) an amino acid, optionally the component e) a nanometal oxide and optionally the component f) an auxiliary are mixed in any desired manner.

The aqueous chloroprene rubber dispersion with high crystallization speed contained in the single-component aqueous spray glue is beneficial to shortening the initial adhesion time of the spray glue; the styrene-acrylate copolymer dispersion is beneficial to shortening the initial adhesion time of spray glue, prolonging the open time and the room-temperature storage stability; the polyol esters and amino acids, which are free of hydroxyl groups, contribute to the storage stability of the spray adhesive without affecting the initial tack of the spray adhesive. The glue spraying agent disclosed by the invention is excellent in spraying property, safe, environment-friendly, good in initial viscosity, long in opening time and excellent in room-temperature storage stability, and the surface of a glue layer formed by glue spraying is dry. The excellent initial viscosity ensures that the spray glue can be bonded in a short time, the bonding efficiency is improved, and the spray glue is particularly suitable for bonding special-shaped surfaces. The long opening time can ensure the long operation time of glue spraying, and the glue spraying of the invention can be used for one-time large-area spraying. The spray glue is particularly suitable for quick bonding between the sponge and the sponge or other substrates.

The single-component water-based spray adhesive can be used in the fields of soft furniture, rail transit and the like.

Detailed Description

The invention provides a single-component water-based spray adhesive, which comprises the following components: a. the shore A hardness increment of the formed adhesive film in 0 hour to 10 hours is more than 90 percent of the shore A hardness increment of the formed adhesive film in 0 hour to 1000 hours; b. a styrene-acrylate copolymer dispersion having an amount of solid components of 15 wt% to 25 wt%, relative to the total weight of the solid components of the aqueous neoprene dispersion; c. a polyol ester free of hydroxyl groups in an amount of 0.9% to 3.8% by weight relative to the total weight of the aqueous spray; d. an amino acid in an amount of 4 wt% to 15 wt%, relative to the total weight of the aqueous neoprene dispersion; e. optionally a nano-metal oxide; and f, optionally an adjuvant. The invention also provides application of the single-component water-based spray adhesive, a product containing a substrate bonded or sealed by the single-component water-based spray adhesive and a bonding method of the single-component water-based spray adhesive.

Single-component water-based spray adhesive

The pH of the one-component aqueous spray gel is preferably 7.0 to 9.0, most preferably 7.6 to 8.0.

Component a) aqueous polychloroprene dispersions

As used herein, "above" and "below" include the present numbers.

The amount of the solid component of the aqueous neoprene dispersion of component a) is preferably 30% to 80% by weight, most preferably 50% to 60% by weight, relative to the total weight of the aqueous neoprene dispersion of component a).

The amount of the aqueous neoprene dispersion is preferably 70% to 80% by weight, relative to the total weight of the spray glue.

Said component a) aqueous polychloroprene dispersion is preferably a linear polymer corresponding to structure I obtained by addition polymerization of 2-chloro-1, 3-butadiene monomers,

the Shore A hardness test method comprises the following steps: pouring the aqueous neoprene dispersoid into a tetrafluoroethylene disc, drying at room temperature for 7 days to prepare an adhesive film with the thickness of 2mm, then overlapping 3 adhesive films with the thickness of 2mm, placing the adhesive films in an oven with the temperature of 90 ℃ for 1 hour to carry out a decrystallization process, taking out the adhesive films, storing for a certain time, testing the Shore A hardness of the adhesive films under the condition of the temperature of minus 5 ℃, and marking the Shore A hardness of the adhesive films at the corresponding time. For example, after the adhesive film is taken out of the oven, the Shore A hardness of the adhesive film is immediately tested at-5 ℃, and the Shore A hardness of the adhesive film is recorded as the Shore A hardness of the adhesive film in 0 hour; taking the adhesive film out of the oven, storing the adhesive film for 10 hours at normal temperature, testing the Shore A hardness of the adhesive film at-5 ℃, and recording the Shore A hardness of the adhesive film for 10 hours; and so on.

If the increase of the Shore A hardness of the adhesive film formed by the aqueous chloroprene dispersion in 0 hour to 10 hours is more than 90% of the increase of the Shore A hardness of the adhesive film in 0 hour to 1000 hours, the crystallization rate of the aqueous chloroprene dispersion is determined to be rapid.

If the increase of the Shore A hardness of the adhesive film formed by the aqueous chloroprene dispersion in 0 hour to 10 hours is less than 90% of the increase of the Shore A hardness of the adhesive film in 0 hour to 1000 hours, and the increase of the Shore A hardness of the adhesive film in 0 hour to 100 hours is more than 90% of the increase of the Shore A hardness of the adhesive film in 0 hour to 1000 hours, the crystallization rate of the aqueous chloroprene dispersion is determined to be medium.

If the increase of the Shore A hardness of the adhesive film formed by the aqueous chloroprene dispersion in 0 hour to 10 hours is less than 90% of the increase of the Shore A hardness of the adhesive film in 0 hour to 1000 hours, and the increase of the Shore A hardness of the adhesive film in 0 hour to 100 hours is less than 90% of the increase of the Shore A hardness of the adhesive film in 0 hour to 1000 hours, the crystallization rate of the aqueous chloroprene dispersion is determined to be slow.

Wherein the increase of the Shore A hardness of the adhesive film in 0 to 10 hours is a value obtained by subtracting the Shore A hardness of the adhesive film in 0 hour from the Shore A hardness of the adhesive film in 10 hours; the increase of the Shore A hardness of the adhesive film in 0 to 100 hours is a value obtained by subtracting the Shore A hardness of the adhesive film in 0 hour from the Shore A hardness of the adhesive film in 100 hours; the increase of the Shore A hardness of the adhesive film in 0 to 1000 hours is the value obtained by subtracting the Shore A hardness of the adhesive film in 0 hour from the Shore A hardness of the adhesive film in 1000 hours.

The aqueous neoprene dispersion preferably has a pH of 10 to 14.

Component b) styrene-acrylate copolymer dispersions

The styrene-acrylate copolymer dispersion preferably has a glass transition temperature of-10 ℃ to 30 ℃, most preferably 10 ℃ to 19 ℃, obtained by measuring the first temperature rise curve by Differential Scanning Calorimetry (DSC) according to DIN65467 at a heating rate of 20K/min.

The amount of the solid component of the styrene-acrylate copolymer dispersion is preferably 40 wt% to 60 wt% relative to the total weight of the styrene-acrylate copolymer dispersion.

The pH of the styrene-acrylate copolymer dispersion is preferably from 7.5 to 9.5, measured at 23 ℃ using a PB-10pH meter from Sartorius, germany.

Component c) polyol esters which do not contain hydroxyl groups

The amount of the polyol ester containing no hydroxyl group is preferably 0.9 wt% to 2.9 wt%, most preferably 0.9 wt% to 2 wt%, relative to the total weight of the one-component water-based spray glue.

The polyol ester containing no hydroxyl group is preferably 2, 4-trimethyl-1, 3-pentanediol diisobutyrate.

Component d) amino acids

The amino acid of the component d) is preferably glycine.

The amount of the amino acid is preferably 4 wt% to 12 wt%, most preferably 4 wt% to 10 wt%, relative to the total weight of the aqueous neoprene dispersion.

Component e) Nano-Metal oxides

The nano metal oxide is preferably one or more of the following: nano zinc oxide powder, nano zinc oxide dispersion, nano magnesium oxide powder and nano magnesium oxide dispersion; further preferred is one or more of the following: nano zinc oxide powder and nano zinc oxide dispersoid; most preferably a nano zinc oxide dispersion.

The amount of the nanometal oxide is preferably 0.1 wt. -% to 5 wt. -%, relative to the total weight of the one-component aqueous spray glue.

Component f) auxiliaries

The auxiliary agent is preferably one or more of the following: antioxidants, light stabilizers, ultraviolet light absorbers, thickeners, mold inhibitors, fillers, defoamers, and pigments.

The amount of antioxidant is preferably 0.1% to 5% by weight, most preferably 0.5% to 3% by weight, relative to the total weight of the one-component water-borne spray glue.

The amounts of light stabilizer and UV absorber are preferably from 0.01% to 5% by weight, most preferably from 0.5% to 3% by weight, each independently, relative to the total weight of the one-component water-based spray adhesive.

The thickener is preferably one or more of the following: polyurethane associative thickeners, acrylic acid alkali swellable thickeners and cellulosic thickeners, most preferably acrylic acid ester alkali swellable thickeners.

The filler is preferably one or more of the following: silica, kaolin and calcium carbonate, most preferably one or more of the following: surface treated kaolin and surface treated silica.

Product(s)

The product is preferably soft furniture, most preferably a sofa, a mattress, a car seat or a train seat.

Bonding method

Between step I and step II of the process there is preferably further included a step iii. Heating and drying the substrate surface to which the one-component aqueous spray-on is applied.

Between step III and step II of the method preferably further comprises a step iv. Irradiating the step III treated substrate surface with actinic radiation.

The substrate is preferably one or more of the following: wood, plastic, metal, glass, textile, alloy, fabric, artificial leather, paper, cardboard, EVA, rubber, leather, glass fiber, ethylene vinyl acetate copolymer, polyolefin, thermoplastic polyurethane, foam, polymer fiber, and graphite fiber, most preferably one or more of the following: polyurethane foam.

The application may be by applying the one-component aqueous spray to the entire surface of the substrate or only to one or more portions of the surface of the substrate.

The application may be brushing, dipping, spraying, rolling, knife coating, flow coating, pouring, printing or transferring, preferably brushing, dipping or spraying.

The heating and drying of the surface of the substrate to which the one-component aqueous spray coating is applied may refer to heating and drying only the surface of the substrate, or may refer to heating and drying a part of or the whole of the substrate including the surface of the substrate to which the one-component aqueous spray coating is applied.

The heating and drying may remove volatile components. The volatile component may be water.

The heating and drying is preferably one or more of: infrared thermal radiation, near infrared thermal radiation, microwaves and the use of convection ovens or spray dryers at elevated temperatures.

Examples

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that the definitions of terms used in this specification conflict with meanings commonly understood by those skilled in the art to which this invention pertains, the definitions set forth herein control.

Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.

As used herein, "and/or" means one or all of the referenced elements.

As used herein, "comprising" and "comprises" encompass the presence of only the recited elements as well as the presence of other, non-recited elements in addition to the recited elements.

All percentages in the present invention are by weight unless otherwise indicated.

The analytical measurements according to the invention were carried out at 23. + -. 2 ℃ unless otherwise stated.

As used in this specification, the terms "a", "an" and "the" are intended to include "at least one" or "one or more" unless otherwise indicated. For example, "a component" refers to one or more components, and thus more than one component may be considered and may be employed or used in the practice of the described embodiments.

The solids content (solids content) of the dispersions was determined in accordance with DIN-EN ISO 3251 using a HS153 moisture meter from Mettler Toledo.

Raw materials and reagents

Dispercoll C84: the aqueous chloroprene dispersion has a high crystallization rate, a solid content of 55 wt% and a pH value of 11-13, and can be purchased from Corsia, germany.

FB80: the aqueous polychloroprene dispersion, which has a rapid crystallization rate, a solids content of 54% by weight and a pH of 11 to 13, is commercially available from Japan electrical chemistry.

Dispercoll C74: aqueous polychloroprene dispersions, medium crystallization rate, solids content of 58% by weight, pH 13, are commercially available from Corcistema, germany.

Revacryl X9045: styrene-acrylic emulsions having a Tg of 12 ℃, a solids content of 50% by weight and a pH value of 8.0 are available from Shanghai Xinte Ma Chemicals, inc.

PRIML AS-2010: styrene-acrylic emulsions, with a Tg of 17 ℃, a solids content of 49% by weight and a pH of 7.8, are commercially available from Dow chemical.

MC-202: the styrene-acrylic emulsion has Tg of 18.5 ℃, a solid content of 47 wt% and a pH value of 9.0, and can be purchased from Beijing Oriental subfamily, chemical engineering and technology Co.

DERMULSENE TR 602: terpene phenolics, 55% solids by weight, pH 8.0, were available from stannless delbrust chemical ltd.

DERMULSENE RA 702: abietic acid, 52% solids by weight, pH 7.0, was available from Standmiyashi chemical Co.

Acronal 7140X: butylbenzene emulsion, 61 wt% solids, pH 7.0, available from basf.

Eastman TXIB:2, 4-trimethyl-1, 3-pentanediol diisobutyrate, available from Istman chemical.

2, 4-trimethyl-1, 3-pentanediol monoisobutyrate: commercially available from eastman chemistry.

Dibutyl sebacate (DBS): commercially available from Yonghua chemical Co., ltd.

Dibutyl phthalate (DBP): commercially available from Yonghua chemical Co., ltd.

Diisobutylphthalate (DIBP): available from Yonghua chemical corporation.

Dibutyl terephthalate (DBT): commercially available from Yonghua chemical Co., ltd.

Dioctyl terephthalate (DOTP): available from Yonghua chemical corporation.

TSR-1068: antioxidants, available from Tongxuan Rixin chemical Co., ltd.

Dnano-233W-30WS: stabilizers, available from Xiamen Nautake technologies, inc.

Glycine: the pH regulator can be obtained from Huayang chemical industry, LLC of Jizhou city.

Boric acid: the pH adjusting agent is available from Yonghua chemical Co., ltd.

Glue spraying performance testing method

pH value: the sprayed glue is placed in a constant temperature water bath at 23 ℃, and a Wantong 913pH meter is used for testing when the temperature is constant at (23 +/-2) ° C.

Phase separation after standing for 1 day at room temperature: and (3) placing the prepared glue spraying sample in a glass bottle for sealed storage for 1 day at the temperature of (23 +/-2) DEG C, and observing the appearance phase separation condition of the sample. The phase separation is qualified, and the phase separation is unqualified.

Storage stability at room temperature: the prepared glue spraying sample is placed in a (23 +/-2) DEG C environment and is stored in a glass bottle in a sealed way, whether the appearance of the glue spraying sample is layered, gelled and the like is observed every other month, a 100-mesh filter screen is used for filtering the glue spraying sample, whether the filtering is smooth is checked, and whether particles, caking and the like are on the filter screen. If the glue spraying sample is stored for 6 months at the temperature of (23 +/-2) DEG C, the appearance has no phenomena of layering, gelation and the like, a 100-mesh filter screen can be used for rapid filtration, and the filter screen has no phenomena of particles, agglomeration and the like, the product is judged to be qualified, otherwise, the product is not qualified.

Initial sticking time: the test sponge was a high resilience polyurethane sponge having dimensions of 9cm by 6cm by 5cm and a density of about 46kg/m ³ . Spraying glue on the surface of sponge with size of 9cm × 6cm, with glue spraying amount of 50g/m ² -60g/m ² (ii) a Starting to oppositely glue from the left along the edge of 6cm, pressing once, if the sponge is not bounced, continuously oppositely gluing towards the right, and repeating the operation; the sponge does not bounce off in the whole bonding process, and the shortest time for the sponge to be completely attached after bonding is the initial bonding time. And recording that the initial viscosity time is not more than 20s as qualified, otherwise, recording that the initial viscosity time is unqualified.

Opening time: the test sponge was a high resilience polyurethane sponge of dimensions 9cm by 6cm by 5cm and a density of about 46kg/m ³ . Spraying glue on the surface of the sponge with the size of 9cm multiplied by 6cm, wherein the glue spraying amount is 50g/m ² -60g/m ² (ii) a Starting to oppositely glue from the left along the edge of 6cm, pressing once, if the sponge is not bounced, continuously oppositely gluing towards the right, and repeating the operation; the sponge does not bounce open in the whole bonding process and is completely attached after being bonded. After the bonded sponge is placed for a certain time, tearing the bonding position of the sponge by hands, and if the bonding position is torn, recording the placing time as the opening time; if the bonding part is not torn and the sponge is broken, the sponge is continuously placed until the bonding part can be torn, and the total time for placing the sponge is recorded as the opening time. And recording the opening time of not less than 20min as qualified, otherwise, recording the opening time as unqualified.

The test environment for initial tack time and open time was 23 ℃ 60% RH.

Table 1 shows the compositions of the spray adhesives of examples 1 to 5 and comparative examples 1 to 7, the performance tests of the spray adhesives, and the evaluation results. Table 2 shows the compositions of the spray adhesives of examples 5 to 10 and comparative examples 8 to 16, the performance tests of the spray adhesives, and the evaluation results.

TABLE 1 spray glue for examples 1 to 5 and comparative examples 1 to 7

Remarking:

1. the amount of the solid component of the styrene-acrylate copolymer dispersion refers to the weight percentage of the solid component of the styrene-acrylate copolymer dispersion relative to the total weight of the solid components of the aqueous neoprene dispersion; when the styrene-acrylate copolymer dispersion is not included in the spray glue component, the amount refers to the weight percentage of the solid components of the terpene phenolic, rosin acid, and styrene-butadiene emulsion in the spray glue relative to the total weight of the solid components of the aqueous neoprene dispersion;

2. the amount of amino acid refers to the weight percentage of amino acid relative to the total weight of the aqueous neoprene dispersion;

3. the amount of boric acid refers to the weight percentage of boric acid relative to the total weight of the aqueous neoprene dispersion.

The single-component aqueous spray adhesives of examples 1-5 of the present invention were satisfactory in terms of room temperature storage stability, and satisfactory in terms of initial adhesion time and open time of the spray adhesive.

Comparing comparative example 1 with examples 1-2, the aqueous spray glue of comparative example 1 comprised an aqueous neoprene dispersion with a moderate crystallization rate and an initial tack time of 60 seconds, failing. It was found that the selection of an aqueous neoprene dispersion with a fast crystallization rate significantly aids the initial tack performance of the spray.

Comparing comparative examples 2-4 and examples 1-3, the aqueous spray-on adhesives of comparative examples 2-4 comprised terpene phenolic, rosin acid, and styrene butadiene emulsion, and failed both the tack time and open time, and the room temperature storage stability of the spray-on adhesive of comparative example 4. As a result, it has been found that the initial tack performance, open time and room temperature storage stability of spray adhesives can be improved by selecting a styrene-acrylate copolymer dispersion.

Comparing comparative examples 5 to 6 with examples 1 and 4 to 5, the amount of the solid component of the styrene-acrylate copolymer dispersion of comparative examples 5 to 6 was 10% by weight and 30% by weight based on the total weight of the solid component of the aqueous chloroprene dispersion, and the initial tack time, open time and room temperature storage stability could not be compatible with the spray coating. As a result, it was found that the initial tack performance, open time and room temperature storage stability can be improved by adjusting the amount of the solid component of the styrene-acrylate dispersion in the spray.

Comparing comparative example 7 with examples 1-5, the spray of comparative example 7 contained boric acid, which failed to meet room temperature storage stability. As a result, glycine in the spray-coated gel was found to improve the storage stability at room temperature.

Remarking:

1. the amount of the solid components of the styrene-acrylate copolymer dispersion refers to the weight percentage of the solid components of the styrene-acrylate copolymer dispersion relative to the total weight of the solid components of the aqueous neoprene dispersion;

2. the amount of amino acid refers to the weight percentage of amino acid relative to the total weight of the aqueous neoprene dispersion;

"/" means that the spray gel phase separates after standing at room temperature for 1 day, and pH, room temperature storage stability, tack time, and open time tests cannot be performed.

The one-component aqueous spray adhesives of examples 5-10 of the present invention were all acceptable in initial tack time, open time, and room temperature storage stability.

Comparing comparative example 8 with examples 5-7, the aqueous spray-on glue of comparative example 8 comprised a polyol ester without hydroxyl groups in an amount of more than 3.8% by weight based on the total weight of the aqueous spray-on glue, and had a short tack time but failed room temperature storage stability. It has been found that the amount of polyol ester having no hydroxyl group in the spray can be suitably adjusted to improve the storage stability at room temperature of the spray.

Comparing comparative examples 9 to 14 with examples 5 to 7, the aqueous spray paints of comparative examples 9 to 14 comprising 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, dibutyl sebacate, phthalate or p-benzoate did not allow compromise between initial tack time, open time and room temperature storage stability of the spray paint, and the spray paints of comparative examples 10, 13 and 14 were allowed to stand at room temperature for 1 day to phase separate and could not be tested for initial tack time, open time and room temperature storage stability. It has been found that the proper amount of polyol ester without hydroxyl groups in the spray can improve the tack time, open time and room temperature storage stability of the spray.

Comparing comparative examples 15-16 with examples 8-10, the aqueous spray-on glues of comparative examples 15-16 contained less than 3.8 wt% glycine of the aqueous neoprene dispersion and the room temperature storage stability of the spray-on glue was not acceptable. The comparison shows that the spray glue not only has short initial adhesion time and long open time, but also has qualified room temperature storage stability by adding proper amount of glycine into the spray glue.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing description, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and therefore any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims (11)

1. A one-component aqueous spray-on glue comprising the following components:

a. the shore A hardness increment of the formed adhesive film in 0 hour to 10 hours is more than 90 percent of the shore A hardness increment of the formed adhesive film in 0 hour to 1000 hours;

b. a styrene-acrylate copolymer dispersion having an amount of solid components of 15 wt% to 25 wt%, relative to the total weight of the solid components of the aqueous neoprene dispersion;

c. a polyol ester free of hydroxyl groups in an amount of 0.9% to 3.8% by weight relative to the total weight of the aqueous spray;

d. an amino acid in an amount of 4 wt% to 15 wt%, relative to the total weight of the aqueous neoprene dispersion;

e. optionally a nano-metal oxide; and

f. optionally an auxiliary agent.

2. The aqueous spray adhesive of claim 1, wherein the component d) amino acid is glycine.

3. The aqueous spray glue according to claim 1 or 2, characterized in that the amount of amino acid is 4-12 wt. -%, most preferably 4-10 wt. -%, relative to the total weight of the aqueous neoprene dispersion.

4. The aqueous spray glue of any one of claims 1 to 3, characterized in that the aqueous polychloroprene dispersion of component a) is a linear polymer according to structure I obtained by addition polymerization of 2-chloro-1, 3-butadiene monomers,

5. the aqueous spray adhesive according to any one of claims 1 to 4, wherein the styrene-acrylate copolymer dispersion has a glass transition temperature of-10 ℃ to 30 ℃, most preferably 10 ℃ to 19 ℃, the glass transition temperature being obtained by Differential Scanning Calorimetry (DSC) according to DIN65467 by measuring the first ramp curve at a heating rate of 20K/min.

6. The aqueous spray-on glue according to any one of claims 1 to 5, characterized in that the amount of the polyol ester containing no hydroxyl groups is between 0.9% and 2.9% by weight, relative to the total weight of the aqueous spray-on glue.

7. The aqueous spray adhesive of any one of claims 1 to 6 wherein said polyol ester containing no hydroxyl group is 2, 4-trimethyl-1, 3-pentanediol dibutyrate.

8. The aqueous spray-on glue of any one of claims 1 to 7, wherein the nano-metal oxide is one or more of the following: nano zinc oxide powder, nano zinc oxide dispersion, nano magnesium oxide powder and nano magnesium oxide dispersion; further preferred is one or more of the following: nano zinc oxide powder and nano zinc oxide dispersoid; most preferably a nano zinc oxide dispersion.

9. Use of the one-component water-based spray glue according to any one of claims 1 to 8 for the preparation of a bonding product.

10. Product comprising a substrate to which a one-component aqueous spray-bonded or sealed according to any of claims 1 to 8 is bonded or sealed.

11. A method of bonding comprising the steps of:

I. applying a one-component water-borne spray glue according to any one of claims 1 to 8 to at least one surface of a substrate; and

contacting the substrate surface treated in step I with the substrate itself or a surface of an additional substrate.