JP7281990B2 - Polyester resin, water repellent composition, and water repellent article - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act 19th Keio Science and Technology Exhibition KEIO TECHNO-MALL 2018, December 14, 2018, Tokyo International Forum Hall E2

The present disclosure relates to polyester resins for attaching microparticles to substrates. TECHNICAL FIELD The present disclosure relates to water repellent compositions for imparting water repellency to substrates. The present disclosure also relates to water repellent articles having water repellency.

A water-repellent agent that treats the surface of an object to make it water-repellent is known (see, for example, Patent Document 1). The water repellent agent described in Patent Document 1 contains silicone oil, hydrophobic metal oxide fine particles having an average particle size of 5 to 20 nm, wax and/or paraffin as a binder for the fine particles, a surfactant, an aqueous solvent and water. , is a spray water repellent with super water repellency.

Japanese Patent No. 4060333

Water-based compositions generally have a lower risk of ignition than oil-based compositions containing organic solvents such as volatile oils. Therefore, the water-based composition can improve the safety of the user compared to the oil-based composition, and can reduce the cost required for safety measures.

In addition, when the base material is highly soluble in organic solvents, the oil-based composition containing the organic solvent cannot be applied to the base material. In such a case, a water-based composition that exhibits the same effect as the oil-based composition is required.

In the spray water repellent described in Patent Document 1, wax and/or paraffin is used as an adhesive (binder) for adhering the metal oxide fine particles to the base material. Since waxes and paraffins are water-insoluble, surfactants are used to disperse them in water repellents. However, since the surfactant is hydrophilic, the desired water repellency cannot be obtained if the added amount is too large. Therefore, it is difficult to prepare a water-based composition imparting water repellency using such an adhesive.

Therefore, an adhesive that can be applied to a water-based composition is desired for adhering oxide fine particles to a substrate.

A first aspect of the present disclosure provides a polyester resin for adhering microparticles to a substrate. The polyester resin contains a polymer of (A) an acid component and (B) an alcohol component. Component (A) comprises 65 mol % to 92 mol % of (A1) first aromatic polycarboxylic acid component containing terephthalic acid component and sulfoisophthalate component, based on the total amount of component (A). 8 mol % to 20 mol % of (A2) a second aromatic polycarboxylic acid component. The (A2) component contains a sodium 5-sulfoisophthalate component and a tetrabutylphosphonium 5-sulfoisophthalate component. Component (B) contains 50 mol % to 90 mol % of ethylene glycol component and 10 mol % to 40 mol % of neopentyl glycol component relative to the total amount of component (B). The polyester resin has a relative viscosity value of 1.33 or greater.

According to a second aspect of the present disclosure, there is provided a water repellent composition containing 3% by mass or more of the polyester resin according to the first aspect, a hydrophobic powder, and an aqueous solvent. The mass ratio of the polyester resin to the hydrophobic powder is 3.5 or less for the hydrophobic powder to 1 part for the polyester resin.

According to the third aspect of the present disclosure, the base material, the polyester resin according to the first aspect arranged on at least a part of the base material, and the polyester resin attached to the base material, at least part of which is made of the polyester resin and an exposed hydrophobic powder.

The polyester resins of the present disclosure can be used to adhere microparticles to substrates. The polyester resins of the present disclosure can be dissolved in water. This allows the polyester resin of the present disclosure to be applied to aqueous compositions.

The water repellent composition of the present disclosure does not require organic solvents (other than alcohol). This makes it possible to apply the water repellent composition of the present disclosure even to oil-soluble substrates. Moreover, by not using a volatile organic solvent, it is possible to enhance the safety of workers against health hazards, fires, and the like. Safety-related costs can be reduced because explosion-proof equipment is not required.

The water repellent article of the present disclosure has high water repellency. The hydrophobic powder exhibiting water repellency is strongly adhered to the substrate.

1 is a schematic cross-sectional view of a water repellent article of the present disclosure; FIG.

Preferred forms of each of the above viewpoints are described below.

According to a preferred embodiment of the first aspect, the (A) component further contains 2 mol % to 15 mol % of the (A3) aliphatic polycarboxylic acid component relative to the total amount of the (A) component. The portion other than the carboxy group in the component (A3) has 2 to 8 carbon atoms. The content of component (A1) is 65 mol % to 92 mol % relative to the total amount of component (A).

According to a preferred embodiment of the first aspect, the (A3) component contains at least one of a succinic acid component and an adipic acid component.

According to a preferred embodiment of the first aspect, the component (A2) contains sodium 5-sulfoisophthalate and tetrabutylphosphonium 5-sulfoisophthalate.

According to a preferred embodiment of the first aspect, the component (A2) comprises 8 mol% to 19.5 mol% of sodium 5-sulfoisophthalate and 0.5 mol% of the total amount of the component (A). ∼5 mol% of tetrabutylphosphonium 5-sulfoisophthalate.

According to a preferred embodiment of the first aspect, the component (B) further contains 3 mol % to 30 mol % of diethylene glycol relative to the total amount of the component (B).

According to a preferred embodiment of the second aspect, the content of the polyester resin is 10% by mass or less with respect to the mass of the water repellent composition.

According to a preferred embodiment of the second aspect, the content of the hydrophobic powder is 0.5% by mass to 10% by mass with respect to the mass of the water repellent composition.

According to the preferred embodiment of the second aspect, the hydrophobic powder is silica powder having an average primary particle size of 5 nm to 100 nm.

According to a preferred embodiment of the second aspect, the aqueous solvent contains at least one of water and lower alcohol.

According to a preferred embodiment of the second aspect, the aqueous solvent contains 30% to 80% by mass of water and 10% to 55% by mass of a lower alcohol, relative to the mass of the water repellent composition. include.

According to a preferred embodiment of the second aspect, the lower alcohol is methanol, ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, 1,2-propanediol, trimethylene glycol, 1,2-butylene. Glycol, 1,3-butylene glycol, glycerin, diethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monotertiary butyl ether , 3-methoxy-3-methylbutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether propionate, diethylene glycol monobutyl ether, and 1,5-pentanediol. including.

According to the preferred embodiment of the second aspect, the surfactant content is 1% by mass or less.

According to a preferred embodiment of the second aspect, the content of the volatile oily component is 5% by mass or less with respect to the mass of the water repellent composition.

According to a preferred embodiment of the third aspect, the total mass of the polyester resin and the hydrophobic powder in the region where the polyester resin and the hydrophobic powder are arranged is 0.1 g to 10 g per 1 m ² of substrate area.

According to a preferred embodiment of the third aspect, the water-repellent article has at least one of flexibility and breathability.

In the following description, reference numerals in the drawings are added for understanding the invention, and are not intended to limit the illustrated embodiments. In addition, the drawings are intended to aid understanding of the silicate coating of the present disclosure, and are intended to limit the silicate coating to the forms of the drawings such as the shape, size, and scale shown. isn't it. In each embodiment, the same elements are given the same reference numerals.

A polyester resin according to the first embodiment of the present disclosure will be described. The polyester resin according to the first embodiment is a polyester resin applicable to attaching fine particles to a substrate.

The polyester resin contains a polymer of (A) an acid component and (B) an alcohol component. In the present disclosure, polymers may also include copolymers composed of two or more types of monomer components (copolymers) and crosslinked polymers (crosspolymers). In the present specification and claims, each acid component and each alcohol component may also include components derived from derivatives (eg, esters) of acid and/or alcohol compounds.

[(A) acid component]
The (A) component includes (A1) a first aromatic polycarboxylic acid component and (A2) a second aromatic polycarboxylic acid component. In the present disclosure, polycarboxylic acid refers to a compound having multiple carboxy groups.

[(A1) First aromatic polycarboxylic acid component]
The (A1) component is an aromatic compound-derived component that does not have a sulfonic acid and/or a salt thereof as a substituent on the aromatic ring. (A1) Component can be, for example, a terephthalic acid component. The terephthalic acid component is preferably the main component of component (A1). The terephthalic acid component can be, for example, 90 mol% or more, 95 mol% or more, 98 mol% or more, or 100 mol% of the total amount of the component (A1).

Component (A1) is, for example, 65 mol% or more, 70 mol% or more, 75 mol% or more, 78 mol% or more, 80 mol% or more, 85 mol% or more, or 90 mol% or more of the total amount of component (A). It can be mol% or more. If the component (A1) is less than 65 mol %, it cannot be used for adhesion of particles. Component (A1) is, for example, 92 mol% or less, 90 mol% or less, 88 mol% or less, 85 mol% or less, 82 mol% or less, 80 mol% or less, or 75 mol% or less of the total amount of component (A). It can be mol % or less. If the component (A1) exceeds 92 mol %, the water solubility will decrease.

[(A2) Second aromatic polycarboxylic acid component]
The (A2) component is an aromatic compound-derived component having a sulfonic acid and/or a salt thereof as a substituent on the aromatic ring. (A2) component includes, for example, a 5-sulfoisophthalic acid derivative component. The 5-sulfoisophthalic acid derivative component is at least one of a sodium 5-sulfoisophthalate component having a sodium sulfonate base and a tetrabutylphosphonium 5-sulfoisophthalate component having a tetrabutylphosphonium sulfonate base. and preferred. The 5-sulfoisophthalic acid derivative component is preferably the main component of component (A2). The 5-sulfoisophthalic acid derivative component can be, for example, 90 mol% or more, 95 mol% or more, 98 mol% or more, or 100 mol% of the total amount of component (A2).

When the polyester resin contains the (A2) component, the polyester resin can be made to exhibit water solubility. On the other hand, as the content of component (A2) increases, the melt viscosity of the polymer excessively increases during the polymerization reaction. It is considered that this is because the interaction between sulfonate groups acts like pseudo-crosslinking, resulting in an excessive melt viscosity higher than the original melt viscosity dependent on the polymer polymerization degree.

Component (A2) can be, for example, 8 mol % or more, 10 mol % or more, or 12 mol % or more of the total amount of component (A). If the (A2) component is less than 8 mol %, the water solubility of the polyester resin becomes too low. Component (A2) is, for example, 25 mol% or less, 22 mol% or less, 20 mol% or less, 15 mol% or less, 13 mol% or less, 12 mol% or less, or 10 mol% or less of the total amount of component (A). It can be mol % or less. If the component (A2) exceeds 25 mol %, the strength of the polyester resin will decrease.

Component (A2) is, for example, among sodium 5-sulfoisophthalate component (hereinafter also referred to as “sodium salt component”) and tetrabutylphosphonium 5-sulfoisophthalate component (hereinafter also referred to as “phosphonium salt component”). Either one or both may be included. By adding the phosphonium salt component, it is possible to suppress an excessive increase in the melt viscosity of the polymer due to pseudo-crosslinking caused by the sodium salt component, and to improve the molecular weight of the polyester resin obtained by synthesis. The molar ratio of the sodium salt component and the phosphonium salt component may be 1 mol or more, 2 mol or more, 3 mol or more, 4 mol or more, or 5 mol or more per 1 mol of the phosphonium salt component. can. The molar ratio of the sodium salt component to the phosphonium salt component can be 7 moles or less, 6 moles or less, 5 moles or less, or 4 moles or less per 1 mole of the phosphonium salt component. The molar ratio is preferably, for example, 3 mol to 5 mol of the sodium salt component per 1 mol of the phosphonium salt component.

When component (A2) contains a sodium salt component and a phosphonium salt component, the sodium salt component is, for example, 8 mol% or more, 9 mol% or more, 10 mol% or more, or It can be 12 mol % or more. The sodium salt component can be, for example, 19.5 mol% or less, 17 mol% or less, 15 mol% or less, 12 mol% or less, or 10 mol% or less with respect to the total amount of component (A). The phosphonium salt component can be, for example, 0.5 mol % or more, 1 mol % or more, 2 mol % or more, 3 mol % or more, or 4 mol % or more with respect to the total amount of component (A). The phosphonium salt component is, for example, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, or 3 mol% or less with respect to the total amount of component (A). can be done.

The (A2) component can contain other acid components within a range that does not inhibit the action of the polyester resin of the present disclosure.

[(A3) Aliphatic polycarboxylic acid component]
The (A) component can further contain (A3) an aliphatic polycarboxylic acid component. Component (A3) is, for example, an aliphatic polycarboxylic acid component having 2 to 8 carbon atoms. Aliphatics can also include cycloaliphatics. The aliphatic polycarboxylic acid component can include, for example, at least one of a succinic acid component, a glutaric acid component, an adipic acid component, a pimelic acid component, a suberic acid, azelaic acid, and a sebacic acid component. By adding the component (A3), the flexibility of the polyester resin can be enhanced. The larger the number of carbon atoms in the aliphatic polycarboxylic acid component, the greater the effect of lowering the glass transition temperature, which in turn leads to lower heat resistance. Therefore, from the viewpoint of the balance between the flexibility of the polyester resin and the glass transition temperature, the component (A3) is preferably an adipic acid component, more preferably a succinic acid component.

The number of carbon atoms in the component (A3) referred to in the present disclosure refers to the number of carbon atoms excluding carboxy groups (e.g., corresponding to the number of methylene groups). For example, succinic acid has two carbon atoms.

Component (A3) can be, for example, 2 mol % or more, 4 mol % or more, 6 mol % or more, or 8 mol % or more of the total amount of component (A). Component (A3) is, for example, 15 mol% or less, 12 mol% or less, 10 mol% or less, 9 mol% or less, 8 mol% or less, or 5 mol% or less of the total amount of component (A). be able to. If the component (A3) exceeds 15 mol %, the glass transition temperature will be low, and there is a risk of softening at room temperature.

The component (A) may contain other acid components as long as they do not inhibit the action of the polyester resin of the present disclosure. Component (A) includes, for example, isophthalic acid component, azelaic acid component, sebacic acid component, 2,6-naphthalenedicarboxylic acid component, 4,4′-biphenyldicarboxylic acid component, 1,12-dodecanoic acid component, 1,2 -cyclohexanedicarboxylic acid component, 1,3-cyclohexanedicarboxylic acid component, 1,4-cyclohexanedicarboxylic acid component, and the like.

[(B) alcohol component]
(B) component contains an aliphatic polyalcohol component. In the present disclosure, polyalcohol refers to a compound having multiple hydroxy groups (polyhydroxy compound).

Component (B) can be, for example, an aliphatic polyalcohol component having 2 to 6 carbon atoms. Component (B) can be, for example, at least one of an ethylene glycol component, a neopentyl glycol component, and a diethylene glycol component. In component (B), the total amount of ethylene glycol component, neopentyl glycol component, and diethylene glycol component is, for example, 90 mol% or more, 95 mol% or more, 98 mol% or more of the total amount of component (B), or It can be 100 mol %.

The ethylene glycol component is, for example, 50 mol% or more, 55 mol% or more, 58 mol% or more, 60 mol% or more, 62 mol% or more, or 65 mol% or more of the total amount of the component (B). can be done. The ethylene glycol component is, for example, 90 mol% or less, 87 mol% or less, 85 mol% or less, 82 mol% or less, 80 mol% or less, 78 mol% or less, 75 mol% of the total amount of the component (B). or less, or 72 mol % or less. By using an ethylene glycol component as a main component, it can be used as an adhesive.

The neopentyl glycol component is, for example, 8 mol% or more, 10 mol% or more, 12 mol% or more, 15 mol% or more, 18 mol% or more, 20 mol% or more, or 22 mol% or more with respect to the total amount of the component (B). It can be mol% or more. If the neopentyl glycol component is less than 8 mol %, the water solubility of the polyester resin will be lowered. The neopentyl glycol component is, for example, 40 mol% or less, 35 mol% or less, 30 mol% or less, 28 mol% or less, 25 mol% or less, 22 mol% or less, or 20 mol% or less with respect to the total amount of the component (B). It can be mol % or less. When the neopentyl glycol component exceeds 40 mol %, the reactivity may be lowered and the productivity may be affected.

The diethylene glycol component can be, for example, 3 mol% or more, 5 mol% or more, 7 mol% or more, or 10 mol% or more with respect to the total amount of the component (B). If the diethylene glycol component is less than 3 mol %, the water solubility will decrease. The diethylene glycol component can be, for example, 30 mol% or less, 28 mol% or less, 25 mol% or less, 22 mol% or less, 20 mol% or less, or 18 mol% or less with respect to the total amount of the component (B). can. If the diethylene glycol component exceeds 30 mol %, the glass transition temperature is lowered, which is not preferable from the viewpoint of heat resistance.

The component (B) can contain other alcohol components as long as they do not inhibit the action of the polyester resin of the present disclosure. Component (B) can further contain, for example, a propylene glycol component, a 1,4-butanediol component, a 1,4-cyclohexanedimethanol component, and the like.

The polyester resin composition of the present disclosure may contain known additives other than those described above within a range that does not impair the effects of the present disclosure. Examples of additives that can be used include polymerization catalysts, antistatic agents, ultraviolet absorbers, heat stabilizers, light stabilizers, release agents, antioxidants, lubricants, plasticizers, pigments, and dyes. Examples of antioxidants include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Among them, hindered phenol-based antioxidants are preferred, and several types may be combined.

[Relative Viscosity Value of Polyester Resin]
The polyester resin of the present disclosure preferably has a relative viscosity value of 1.33 or more. If the relative viscosity value is less than 1.33, the strength of the polyester resin coating film becomes too low. The relative viscosity value of the polyester resin can be 1.80 or less.

The relative viscosity value shown in the present disclosure is obtained by dissolving 0.5000 ± 0.0005 g of a sample in 50 ml of a mixed solvent of phenol: tetrachloroethane = 60: 40 (mass ratio), and attaching an Ubbelohde viscosity tube at a solution temperature of 20 ° C. It can be measured using an automatic viscometer.

[Glass transition temperature of polyester resin]
The glass transition temperature of the polyester resins of the present disclosure can be 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher. The glass transition temperature of the polyester resin of the present disclosure can be, for example, 110° C. or lower.

The glass transition temperature referred to in the present disclosure refers to the midpoint temperature of endothermic behavior due to glass transition in Differential Scanning Calorimetry (DSC).

[Water solubility of polyester resin]
The polyester resin of the present disclosure has solubility in water (water solubility). The term “water-soluble” as used in the present disclosure means that the polyester resin can be dissolved in hot water of 80° C. or higher so that the polyester resin concentration is 10% by mass or more.

[Method for producing polyester resin]
A method for producing a polyester resin according to the first embodiment of the present disclosure will be described. The polyester resins of the present disclosure can be produced by known methods.

First, for example, an ester prepolymer is produced by a direct esterification reaction between an acid component and an alcohol component, or a transesterification reaction between an ester derivative of an acid component (for example, a dimethyl ester compound of an acid component) and an alcohol component. The mixing ratio of the acid component and the alcohol component is appropriately adjusted so as to obtain the content ratio shown in the polyester resin of the present disclosure described above. Usually, an alcohol component is added in excess to the acid component, and after the esterification reaction or transesterification reaction, the excess glycol is distilled off by vacuum polymerization to obtain a polymer having a predetermined molecular weight. The excess ratio of the alcohol component can be set so that the molar ratio of the total alcohol component to the total acid component is approximately 1.05 to 2.50. In the esterification reaction or transesterification reaction, for example, raw materials are charged into a reaction tank equipped with a heating device, a stirrer and a distillation tube, a reaction catalyst is added as necessary, and the mixture is stirred under an inert gas atmosphere at atmospheric pressure. It can be carried out by heating and allowing the reaction to proceed while distilling off by-products such as water and methanol produced by the reaction. The reaction temperature can be, for example, 150°C to 270°C, preferably 220°C to 260°C. The reaction time can be, for example, 3 to 7 hours. For the polyester resin of the present disclosure, the esterification reaction is preferably selected from the viewpoint of production efficiency.

In general, the synthesis of a polyester resin is accompanied by generation of diethylene glycol as a polymer of ethylene glycol as a side reaction. Especially when a sulfonic acid group-containing monomer is used as in the present disclosure, the side reaction of diethylene glycol appears remarkably. can be controlled. Examples of organic bases include sodium hydroxide, sodium acetate, tetraethylammonium hydroxide and the like. The amount of the organic base to be added is preferably 50 ppm to 3000 ppm with respect to the mass of the polyester resin to be produced.

As a catalyst for the transesterification reaction, one or more known metal compounds such as sodium, potassium, calcium, titanium, lithium, magnesium, manganese, zinc, tin and cobalt can be used. In the case of transesterification, calcium compounds and manganese compounds are particularly preferred from the viewpoint of reactivity and the color tone of the resulting resin. The amount of the transesterification catalyst added can be, for example, 5 ppm to 1000 ppm, preferably 10 ppm to 500 ppm, based on the mass of the polyester resin to be produced.

In order to facilitate the subsequent polymerization step, it is preferable to add the phosphorus compound after the esterification reaction or transesterification reaction is completed. Phosphorus compounds include, for example, phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite and the like. Among these, phosphoric acid or triethyl phosphate is more preferable. The amount of the phosphorus compound added can be, for example, 10 ppm to 2000 ppm, preferably 20 ppm to 1500 ppm, based on the mass of the polyester resin to be produced.

Then, following the transesterification or esterification reaction, a polymerization catalyst can be added to the ester prepolymer and further polycondensation reactions can be carried out until the desired molecular weight is achieved. The pressure in the tank can be reduced, for example, from a normal pressure atmosphere to 2.6 kPa or less, preferably 1.3 kPa or less. The temperature in the bath can be gradually increased from, for example, 220 to 250.degree. C. and finally to 250 to 290.degree. C., preferably 260 to 280.degree. After the melt viscosity reaches a predetermined torque, the reactants can be extruded and collected from the bottom of the vessel. For example, the reaction product can be extruded in water in the form of a strand, cooled and cut to obtain a polyester resin in the form of pellets.

A known catalyst can be used as the polymerization catalyst. Preferred polymerization catalysts include, for example, metal compounds such as titanium, germanium, antimony and aluminum. Titanium compounds and germanium compounds are particularly preferred from the viewpoints of reactivity, safety of the catalytic substance to living organisms, and color tone. The amount of the polymerization catalyst added can be, for example, 10 ppm to 1000 ppm, preferably 100 ppm to 800 ppm, based on the mass of the polyester resin to be produced.

In the method for producing the polyester resin of the present disclosure, various additives such as lubricants, release agents, heat stabilizers, antistatic agents, plasticizers, ultraviolet absorbers, and pigments are appropriately blended according to the application and molding purpose. be able to. These additives may be blended in either the reaction process or the molding process.

The polyester resin according to the first embodiment can strongly adhere the powder to the substrate. That is, according to the polyester resin according to the first embodiment, it is possible to prevent the powder from peeling off from the substrate.

Since the polyester resin according to the first embodiment is water-soluble, it can be applied to aqueous compositions. For example, the polyester resin according to the first embodiment can be added as an adhesive in the water repellent composition according to the second embodiment.

In the aqueous composition, the polyester resin according to the first embodiment can also act as a powder dispersant. In the aqueous composition, the polyester resin according to the first embodiment can also act as a thickening agent.

A coating film formed using the polyester resin according to the first embodiment has flexibility. For example, the polyester resin according to the first embodiment can be applied to flexible substrates.

A water repellent composition according to a second embodiment of the present disclosure will be described. The water repellent composition can impart water repellency to the substrate when applied to the substrate and dried.

A water repellent composition according to the second embodiment includes the polyester resin according to the first embodiment, hydrophobic powder (hydrophobic particles), and an aqueous solvent.

[Polyester resin]
Regarding the polyester resin in the water repellent composition, the above description is used, and the description is omitted here. In the water repellent composition according to the second embodiment, the polyester resin according to the first embodiment acts as an adhesive that adheres the hydrophobic powder (particles) to the substrate. Moreover, the polyester resin is considered to act as a dispersant for dispersing the hydrophobic powder (particles) in the water repellent composition. It is believed that the polyester resin acts as a thickening agent in the water repellent composition.

The content of the polyester resin in the water repellent composition is, for example, 3% by mass or more, 4% by mass or more, 5% by mass or more, or 6% by mass or more with respect to the mass of the water repellent composition. can be done. If the polyester resin content is less than 3% by mass, it becomes difficult to firmly adhere the hydrophobic powder to the substrate. The content of the polyester resin in the water repellent composition is, for example, 12% by mass or less, 10% by mass or less, 8% by mass or less, or 6% by mass or less with respect to the mass of the water repellent composition. can be done. If the polyester resin content exceeds 12% by mass, the hydrophobic powder is coated with the polyester resin, making it impossible to exhibit water repellency.

[Hydrophobic powder]
Hydrophobic powder (hydrophobic particles) is for making the base material exhibit water repellency after the water repellent composition is applied to the base material and dried. The hydrophobic powder may be an inorganic substance or an organic substance as long as it can exhibit water repellency. Examples of inorganic powders that can be used include silica, alumina, and titania. The hydrophobic powder may be inorganic substrate particles and/or organic substrate particles whose surfaces are coated with a water-repellent substance (for example, a silane coupling agent). The hydrophobic powder may be powder obtained by hydrophobizing the surface of hydrophilic particles.

The average primary particle size of the hydrophobic powder can be, for example, 5 nm or more. The average primary particle size of the hydrophobic powder can be, for example, 100 nm or less, 50 nm or less, or 20 nm or less. The particle shape in the hydrophobic powder can be spherical, for example.

Commercially available hydrophobic powders include Aerosil R972, 972V, R972CF, R974, R812, R805, RX200, RX300, and RY200 (all of which are hydrophobic silica) manufactured by Nippon Aerosil Co., Ltd. Among them, Aerosil R972 and RX200 are preferable.

The content of the hydrophobic powder in the water repellent composition is, for example, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, relative to the mass of the water repellent composition. It can be 4% by mass or more, 5% by mass or more, or 6% by mass or more. If the hydrophobic powder is less than 0.5% by mass, it is not possible to impart sufficient water repellency to the substrate. The content of the hydrophobic powder in the water repellent composition is, for example, 10% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, or 5% by mass or less with respect to the mass of the water repellent composition. % by mass or less. If the hydrophobic powder content exceeds 10% by mass, the adhesion of the coating film to the substrate will decrease.

[Mass ratio of polyester resin and hydrophobic powder]
The mass ratio of the polyester resin and the hydrophobic powder in the water repellent composition is 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.5 or more, and 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, and 0.5 or more. It can be 6 or more, 0.8 or more, or 1 or more. If the amount of the hydrophobic powder is too small relative to the amount of the polyester resin, the amount of the hydrophobic powder exposed from the polyester resin is reduced, resulting in a decrease in water repellency. The mass ratio of the polyester resin to the hydrophobic powder in the water repellent composition is 3.5 or less, 3 or less, 2.5 or less, 2 or less, 1.8 or less, 1 It can be 0.5 or less, 1.2 or less, or 1 or less. Too much hydrophobic powder relative to the amount of polyester resin results in hydrophobic powder not adhering to the substrate.

[Aqueous solvent]
Any aqueous solvent may be used as long as it can serve as a medium for coating or applying the hydrophobic powder to the substrate. The aqueous solvent is preferably one that does not dissolve the hydrophobic powder and one that does not react with the hydrophobic powder. The aqueous solvent can contain at least one of water and lower alcohols. Lower alcohols are monoalcohols and/or polyalcohols having 6 or less carbon atoms. Examples of lower alcohols include methanol, ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, 1,2-propanediol (propylene glycol), trimethylene glycol, 1,2-butylene glycol, 1,2-butylene glycol, 3-butylene glycol, glycerin, diethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol (hexylene glycol), ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol Monobutyl Ether (Butyl Cellosolve), Ethylene Glycol Monotertiary Butyl Ether (ETB), 3-Methoxy-3-methylbutanol (Solfit®), 1-Methoxy-2-propanol (PGM), 1-ethoxy-2-propanol (PE), propylene glycol monomethyl ether propionate (methotate), diethylene glycol monobutyl ether (butyl diglycol), and at least one selected from the group consisting of 1,5-pentanediol (pentamethylene glycol). . Among these, for example, the aqueous solvent can include at least one of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and ethanol. Aqueous solvents can include both water and lower alcohols.

The content of water in the water repellent composition can be, for example, 30% by mass or more, 35% by mass or more, or 40% by mass or more with respect to the mass of the water repellent composition. The content of water in the water repellent composition is, for example, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less with respect to the mass of the water repellent composition. , 55% by mass or less, or 50% by mass or less.

The content of the lower alcohol in the water repellent composition can be, for example, 10% by mass or more, 15% by mass or more, or 20% by mass or more with respect to the mass of the water repellent composition. The content of the lower alcohol in the water repellent composition is, for example, 55% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less with respect to the mass of the water repellent composition. can be done.

The content of the aqueous solvent in the water repellent composition can be, for example, 70% by mass or more, 75% by mass or more, or 80% by mass or more with respect to the mass of the water repellent composition. The content of the aqueous solvent in the water repellent composition is, for example, 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less with respect to the mass of the water repellent composition. can be done.

The water repellent composition can contain no highly flammable volatile oily component (organic solvent) (no lower alcohol). The content of the volatile oil component in the water repellent composition can be, for example, 5% by mass or less, 3% by mass or less, or 1% by mass or less with respect to the mass of the water repellent composition, Preferably, the water repellent composition contains substantially no volatile oily components. By not containing a volatile oily component, safety can be enhanced and the cost for ensuring safety can be reduced.

In the water repellent composition of the present disclosure, the hydrophobic powder is adhered to the substrate with the polyester resin according to the first embodiment. Therefore, no water-insoluble (hydrophobic) adhesive such as wax or paraffin is required for adhering the hydrophobic powder. The content of the water-insoluble adhesive in the water repellent composition is, for example, 1% by mass or less, 0.5% by mass or less, or 0.1% by mass or less with respect to the mass of the water repellent composition. can do. Preferably, the water repellent composition contains substantially no water-insoluble adhesives. If the content of water-insoluble adhesive is small, the amount of surfactant added can be reduced. This makes it possible to suppress the decrease in water repellency caused by the surfactant.

The content of the surfactant in the water repellent composition is, for example, 1% by mass or less, 0.5% by mass or less, or 0.1% by mass or less with respect to the mass of the water repellent composition. can be done. Preferably, the water repellent composition is substantially free of surfactants. This is because, if the content of the surfactant is high, the hydrophilic effect increases and the water repellency decreases.

A method for producing a water repellent composition according to the second embodiment of the present disclosure will be described.

The water repellent composition according to the second embodiment can be produced by mixing the components described above. For example, a method for producing a water repellent composition can first have a step of preparing an aqueous solution of the polyester resin according to the first embodiment. For the aqueous solution of the polyester resin, for example, a mixture of water and the polyester resin may be heated to dissolve the polyester resin in the water, or the polyester resin may be added to water at 80°C or higher to dissolve the polyester resin in the water. good too. The method for producing the water repellent composition can then have a step of adding and mixing a hydrophobic powder and an aqueous solvent to the aqueous polyester resin solution. Thereby, a water repellent composition can be produced. The order of mixing is not limited to the order described above, and any order can be selected.

According to the water repellent composition of the present disclosure, water repellency can be imparted to the substrate region to which the water repellent composition is applied. Although the water repellent composition of the present disclosure is an aqueous composition, the hydrophobic powder can be strongly adhered to the substrate. That is, according to the water repellent composition of the present disclosure, a highly durable water repellent coating can be formed on a substrate.

In the water repellent composition of the present disclosure, the polyester resin according to the first embodiment adheres the hydrophobic powder to the substrate. This eliminates the use of non-water soluble adhesives such as waxes and paraffins to adhere the hydrophobic powder to the substrate. Therefore, a surfactant for dispersing the non-crystalline adhesive is not necessarily required, or the content of the surfactant can be reduced. As a result, the decrease in water repellency can be suppressed due to the hydrophilicity provided by the surfactant.

The water repellent composition of the present disclosure does not require volatile oily components (eg, toluene, methyl ethyl ketone, etc.). Therefore, the water repellent composition of the present disclosure, as compared to the oil-based water repellent composition containing such a volatile oil component, the worker's health damage caused by the volatile gas, the risk of ignition of the volatile gas, etc. Safety can be improved. According to the water repellent composition of the present disclosure, explosion-proof equipment is not required in the usage environment, so safety-related costs can be reduced. In addition, since it is not necessary to use an oily solvent, it is possible to easily treat the waste liquid generated by the coating process, and reduce the cost required for the waste liquid treatment.

The water repellent composition of the present disclosure does not require a volatile oily component. This facilitates the treatment of waste liquid during production and/or use of the water repellent composition.

The water repellent composition of the present disclosure can be applied to substrates with low resistance to organic solvents.

A water repellent coating made from the water repellent composition of the present disclosure can have transparency. For example, a water-repellent coating can be formed so that the design of the substrate can be seen. The water repellent composition of the present disclosure can also be applied when producing a transparent water repellent article.

A water-repellent article according to a third embodiment of the present disclosure will be described. FIG. 1 shows a schematic cross-sectional view of a water-repellent article of the present disclosure. The water-repellent article 10 is an article having at least part of the surface treated for water repellency. For example, the water repellent article 10 is an article having at least part of its surface treated with the water repellent composition according to the second embodiment.

A water-repellent article 10 according to the third embodiment includes a substrate 1, a polyester resin 2 disposed on at least a part of the substrate 1, a hydrophobic powder 3 attached to the substrate 1 by the polyester resin 2, Prepare.

For the base material 1, for example, metal, ceramic, glass, resin, cloth, paper, etc. can be selected according to the application and/or purpose. The shape and/or dimensions of the substrate 1 are also not particularly limited. The substrate 1 can be, for example, plate-like, porous, fibrous, or the like.

The polyester resin 2 can be the polyester resin according to the first embodiment. Regarding the polyester resin 2, the above description is incorporated. The polyester resin 2 can be present on the substrate 1 in the form of a film. The average film thickness of the polyester resin 2 is preferably equal to or less than the average particle size of the hydrophobic powder 3 .

The hydrophobic powder 3 can be the hydrophobic powder in the water repellent composition according to the second embodiment. Regarding the hydrophobic powder 3, the above description is incorporated. Hydrophobic powder 3 is adhered to substrate 1 by polyester resin 2 . At least part of the hydrophobic powder 3 is exposed from the polyester resin 2 . That is, when the water-repellent article 10 gets wet with water, at least part of the hydrophobic powder 3 is configured to come into contact with water.

In the area where the water-repellent coating containing the polyester resin 2 and the hydrophobic powder ³ is formed, the density of the water-repellent coating is preferably 0.1 g or more, preferably 0.5 g or more, per 1 m 2 of area. More preferably, it is 0.8 g or more. The density of the water-repellent coating should be 1 g or more, 1.5 g or more, 2 g or more, 2.5 g or more, 3 g or more, 3.5 g or more, 4 g or more, 4.5 g or more, or 5 g or more ^per square meter of area. can be done. The density of the water-repellent coating can be 7 g or less, 6 g or less, 5 g or less, 4 g or less, 3 g or less, 2.5 g or less, 2 g or less, 1.5 g or less, or 1 g or less per square meter ^of area.

Each content of the polyester resin 2 and the hydrophobic powder 3 in the water repellent film (each density of the polyester resin 2 and the hydrophobic powder 3) is determined from the mass ratio of the polyester resin and the hydrophobic powder in the water repellent composition. can be calculated.

If it is impossible to directly specify the distribution amount of the polyester resin 2 and/or the hydrophobic powder 3 per unit area (the density of the water-repellent coating) from the structure or characteristics of the water-repellent article 10, the repellent It should be allowed to specify by the manufacturing method of the aqueous article, that is, to calculate the distribution amount of the polyester resin 2 and/or the hydrophobic powder 3 from the coating amount of the water repellent composition per unit area. That is, the distribution amount of the polyester resin 2 and / or the hydrophobic powder 3 per unit area is, for example, the coating amount of the water repellent composition, and the hydrophobic powder 3 and / or the polyester resin 2 in the water repellent composition can be calculated from the content of (and the mass ratio of the polyester resin and the hydrophobic powder).

The contact angle of water in the region where the hydrophobic powder 3 is arranged in the water-repellent article 10 according to the third embodiment can be 135 degrees or more, 140 degrees or more, 145 degrees or more, or 150 degrees or more. The contact angle of water is determined, for example, by dropping a 10 μL water droplet on the object to be measured by the static drop method in accordance with JISR3257, and capturing the angle formed by the tangent line and the horizontal line at the contact point between the object and the water droplet with a microscope or digital camera. It can be measured by image analysis.

A method for manufacturing a water repellent article according to the third embodiment of the present disclosure and a method for using the water repellent composition according to the second embodiment will be described. The method for producing a water repellent article includes steps of preparing a substrate 1, steps of preparing a water repellent composition according to the second embodiment, steps of applying the water repellent composition to the substrate 1, and and a step of drying the substrate 1 to which the liquid medication composition has been applied.

The method of applying the water repellent composition is not particularly limited, and known coating methods, film-forming methods, and the like can be used. For example, the water repellent composition can be applied to the substrate by spraying, spin coating, dipping, a roller, a brush, or the like. Before applying the water repellent composition to the substrate 1, it may be concentrated or diluted depending on the application and/or purpose. Dilution can be performed, for example, with an aqueous solvent as described above.

The drying method is not particularly limited as long as it is a method that does not adversely affect the hydrophobic powder 3 and the polyester resin 2 applied to the base material 1 and the base material 1 . For example, the water repellent composition can be dried by natural drying, heating, air blowing, or the like.

The coating amount of the water repellent composition per unit area is adjusted so as to obtain the desired distribution density of the polyester resin 2 and/or the hydrophobic powder 3 (the density of the water repellent coating). can be determined according to

The water repellent article according to the third embodiment has high water repellency. The water repellency of the water repellent article according to the third embodiment has persistence (durability). In addition, the water-repellent coating prepared from the water-repellent composition of the present disclosure has flexibility, and can maintain water repellency even when the substrate has flexibility. That is, the water repellent article can have flexibility. Moreover, since the water-repellent film has transparency, the water-repellent article can also have transparency. When the substrate has air permeability, the water repellent article can have air permeability depending on the form of the water repellent coating.

It may be difficult or nearly impractical to directly identify the polyester resins, water repellent compositions and water repellent articles of the present disclosure by virtue of their composition, structure, properties, and the like. In such cases, it should be allowed to specify the polyester resin, water repellent composition and water repellent article of the present disclosure by these manufacturing methods.

The polyester resin, the water repellent composition, the water repellent article, and the method for producing these of the present disclosure will be described below with examples. However, the polyester resin, the water repellent composition, the water repellent article, and the production method thereof are not limited to the following examples.

[Test Examples 1 to 14]
Polyester resins of the present disclosure were prepared and measured for composition, relative viscosity values, and glass transition temperatures. Moreover, the solubility in water of each polyester resin was confirmed. The measurement method for each evaluation item will be described below. Table 1 shows the composition and evaluation of each polyester resin.

[Manufacturing of polyester resin]
Into a reactor equipped with a stirrer, a distillation tube and a decompression device, each carboxylic acid compound of the component (A) other than the sulfonate-containing aromatic dicarboxylic acid component (A2) and the alcohol compound of the component (B) are charged. , and after purging with nitrogen, the temperature was raised from 150° C. to 230° C. over 2 hours. Thereafter, the esterification reaction was carried out for 5 hours while raising the internal temperature from 230°C to 260°C. Reaction water generated by the esterification was taken out of the system through a distillation tube and collected. The theoretically calculated amount of reaction water was compared with the actual amount of distilled reaction water, and a reaction water amount of 90% or more was used as a standard for completion of the esterification reaction. Subsequently, 30 ppm of phosphoric acid, 300 ppm of germanium dioxide, and (A2) sulfonate-containing aromatic dicarboxylic acid component and an ester derivative of ethylene glycol were added to the mass of the polyester resin to be produced to initiate a polycondensation reaction. After 90 minutes, the pressure was reduced to 2.6 kPa or less, the internal temperature was raised from 250° C. to 270° C. during this time, and the polycondensation reaction was performed by stirring until a predetermined viscosity was reached under vacuum of 1.3 kPa or less. . The resulting polyester resin was extruded into strands in water and cut into pellets. Table 1 shows the composition and evaluation properties of the obtained polyester resin. In Table 1, each compound is represented by the above abbreviation. However, diethylene glycol is a by-product produced by the esterification process.

[composition]
A proton NMR spectrum of the polyester resin was measured to quantify the content of each component in the polyester resin.

[Relative viscosity]
The relative viscosity value of each composition was obtained by adding each composition A solution is prepared by dissolving 0.5000 ± 0.0005 g of the substance, and the ratio of the flowing time of the test solution to the flowing time of the solvent at 20 ° C. using an automatic viscometer equipped with an Ubbelohde viscosity tube (test solution It was obtained from (flow time of the solvent/flow time of the solvent).

[Glass transition temperature (Tg)]
10 mg of the polyester resin composition was weighed, and the polyester resin sample was held isothermally at 270° C. for 3 minutes in a nitrogen atmosphere using a scanning differential calorimeter DSC, and heated from 270° C. to 0° C. at 200° C./min. After cooling, the endothermic behavior was observed while the temperature was raised from 0° C. at a rate of 10° C./min.

[Solubility in water]
Add 90% by mass of water and 10% by mass of polyester resin to an Erlenmeyer flask with a cooling tube containing a stirrer, and stir with a magnetic stirrer with a temperature control function to boil (100 ° C.). It was confirmed whether all of the polyester resin could be dissolved. Evaluation criteria are shown below.
A: all of the polyester resin dissolved in water;
B: A polyester resin that was not dissolved in water remained.

[Adhesiveness]
A polyester resin aqueous solution was prepared by dissolving a polyester resin in water having a temperature of 80° C. or higher so as to have a concentration of 10% by mass. A polyester resin aqueous solution was applied to a polyester film substrate to form a polyester resin film of 15 g/m ² . After sticking Cellotape (registered trademark) 12 mm (Nichiban: CT-12) specified in JISZ1522 (2009) to the formed polyester resin film, the Cellotape was peeled off, and the presence or absence of peeling of the polyester resin film on the substrate was confirmed. . Evaluation criteria are shown below.
A: The polyester resin was hardly peeled off from the substrate;
B: The polyester resin was slightly peeled off from the substrate;
C: Most of the polyester resin was peeled off from the substrate.

[Flexibility]
In the same manner as in the adhesion test, a polyester resin film was formed on a polypropylene nonwoven fabric substrate having flexibility, and it was confirmed whether the flexibility of the substrate was maintained. Evaluation criteria are shown below.
A: The substrate on which the polyester resin film was formed had the same flexibility as the substrate itself;
B: The substrate on which the polyester resin film was formed was slightly harder than the substrate;
C: Cracking or peeling occurred in the polyester resin film.

The polyester resins of Test Examples 1 and 2, which contain 8 mol% or less of sodium 5-sulfoisophthalate, which is the second aromatic polycarboxylic acid, and do not contain neopentyl glycol, have solubility in water. I didn't. However, in Test Examples 3 to 14 in which 5-sodium sulfoisophthalate is 8 mol% or more and neopentyl glycol is added to the alcohol component in an amount of 10 mol% or more, the polyester resin can have solubility in water. rice field. From this, in order to ensure the water solubility of the polyester resin, it is considered preferable that the second aromatic polycarboxylic acid component is 8 mol % or more with respect to the total amount of the acid components. It is believed that the second aromatic polycarboxylic acid component can be 25 mole percent or less of the total amount of acid components. Neopentyl glycol is considered to be preferably 8 mol % or more with respect to the total amount of alcohol components.

In Test Example 3, even when the second aromatic polycarboxylic acid was a sodium 5-sulfoisophthalate component (sodium salt component) alone, it was possible to ensure water solubility. In Test Examples 4 to 5 and 7 to 14, when a tetrabutylphosphonium 5-sulfoisophthalate component (phosphonium salt component) was further added in addition to the sodium salt component, peeling occurred as shown in Test Examples 15 to 36 below. It was possible to increase the resistance to the test. From this, it is considered preferable that the phosphonium salt component is 0.5 mol % or more with respect to the total amount of the acid component. It is believed that the phosphonium salt component can be up to 8 mole percent of the total acid component. It is believed that the proportion of sodium salt component can be one or more times that of the phosphonium salt component. It is believed that the proportion of sodium salt component can be up to 7 times that of the phosphonium salt component.

The polyester resin of Test Example 6 had a relative viscosity value of less than 1.33, and in Test Example 22 described later, the polyester resin of Test Example 6 had low adhesiveness to the substrate. From this, it is considered preferable that the relative viscosity value of the polyester resin is 1.33 or more.

The polyester resins of Test Examples 9-14, to which succinic acid and/or adipic acid was added as the aliphatic polycarboxylic acid component, were able to increase flexibility more than the polyester resins of Test Examples 3-8. In particular, the polyester resins of Test Examples 9 to 12 and 14 to which succinic acid was added were able to improve the adhesiveness. Accordingly, the content of the aliphatic polycarboxylic acid component having 2 to 8 carbon atoms is preferably 2 mol % or more relative to the total amount of the acid component. In Test Examples 9 to 12, when the amount of succinic acid added was reduced, the glass transition temperature tended to rise. From this, in order to increase the heat resistance of the polyester resin, the aliphatic polycarboxylic acid component having 2 to 8 carbon atoms is preferably 20 mol% or less, and 15 mol% or less, relative to the total amount of the acid component. , more preferably 10 mol % or less, and more preferably 8 mol % or less.

[Test Examples 15 to 36]
A water repellent composition was prepared using the polyester resin of the above test example. Each water repellent composition was tested for water repellency after formation of the water repellent film and water repellency after the peeling test.

A polyester resin aqueous solution was prepared by adding a polyester resin to water heated to 80° C. or higher. Next, each component of the hydrophobic silica and the aqueous solvent was added to the polyester resin aqueous solution and mixed. Thus, a water repellent composition was produced. Tables 3 to 5 show the composition according to each test example. The blending ratio is expressed in % by mass. Hydrophobic silica having an average primary particle size of 12 nm was used as the hydrophobic powder. The numbers in parentheses of the polyester resins in Tables 3 to 5 indicate the test example numbers of Test Examples 1 to 14 above. That is, the polyester resin used in Test Examples 16 to 21 is the polyester resin of Test Example 3. The polyester resin used in Test Example 22 is the polyester resin of Test Example 6. The polyester resin used in Test Examples 23-26 is the polyester resin of Test Example 9. The polyester resin used in Test Examples 27 and 28 is the polyester resin of Test Example 11. The polyester resins used in Test Examples 29-36 are the polyester resins of Test Examples 4, 5, 7, 8, 10, 12, 13 and 14, respectively. At least one of water, diethylene glycol monobutyl ether (abbreviated as "BDG" in the table), ethylene glycol monobutyl ether (abbreviated as "BG" in the table), and ethanol was used as the aqueous solvent.

The prepared water repellent composition was applied to a polyester film substrate using a coater bar No. 6 so that the coating amount was 2.5 g/m ² and dried to form a water repellent coating having a uniform thickness. was coated (corresponding to the water-repellent article of the present disclosure).

[Water repellency test]
10 μL of water was dropped on the water-repellent coating, and the contact angle of water with respect to the water-repellent coating was measured using a contact angle meter (CA-DT manufactured by Kyowa Interface Science Co., Ltd.). The water repellency of the water repellent film was evaluated according to the following criteria.
A: The contact angle was 150 degrees or more;
B: The contact angle was 135 degrees or more and less than 150 degrees;
C: The contact angle was less than 135 degrees.

[Water repellency test after peeling]
Next, a 12 mm cellotape (registered trademark) (Nichiban: CT-12) was attached to the water-repellent film on the polyester film substrate, and then removed. If the tape removes the hydrophobic silica from the substrate, the water repellency is reduced. On the other hand, when the hydrophobic silica is firmly adhered to the base material by the polyester resin and remains on the base material, the water repellency is maintained. Therefore, water droplets were dropped with a dropper onto the area from which the tape had been removed, and the water repellency of the water repellent film was evaluated according to the following criteria.
A: All water was repelled at the locations where the water droplets were dropped. ;
B: Adhesion of water was observed at a part of the place where water droplets were dropped;
C: Adhesion of water was observed at all locations where water droplets were dropped.

High water repellency was obtained in the water repellent article produced from the water repellent composition according to Test Example 15 containing 2% by mass of hydrophobic silica. From this, it is considered that the water repellent powder is preferably 0.5 mass % or more, more preferably 1 mass % or more, relative to the mass of the water repellent composition. Also, hydrophobic silica could be blended up to at least 5% by mass.

However, in Test Example 15 in which the polyester resin was not blended, the hydrophobic silica was peeled off from the substrate by the tape peeling, so water repellency after the peeling test was not obtained. Also in Test Example 17 in which 2% by mass of the polyester resin of the present disclosure was blended, no water repellency was obtained after the peel test. On the other hand, in Test Example 18 in which 4% by mass of the polyester resin of the present disclosure was blended, sufficient water repellency was obtained even after the peel test. It is believed that this is because the polyester resin of the present disclosure could suppress the peeling of the hydrophobic silica. From this, it is considered that the polyester resin of the present disclosure is preferably 3% by mass or more, more preferably 4% by mass or more, relative to the mass of the water repellent composition. Moreover, the polyester resin could be blended up to at least 9% by mass.

In Test Example 16, sufficient water repellency was not obtained even when 2% by mass of hydrophobic silica was blended. This is probably because the amount of the polyester resin was larger than the amount of the hydrophobic silica, so that the hydrophobic silica was coated with the polyester resin and the exposed amount of the hydrophobic silica was reduced. On the other hand, none of the water repellent articles produced from the water repellent compositions according to Test Examples 17 to 36 had any problem in water repellency. In Test Examples 17 to 36, it is believed that at least part of the fine particles of hydrophobic silica are exposed from the polyester resin in the substrate. From this, it is considered that the mass ratio of the polyester resin to the hydrophobic powder in the water repellent composition is preferably 3.5 or less, and more preferably 3 or less, relative to the polyester resin 1. . It is considered that the mass ratio of the polyester resin to the hydrophobic powder in the water repellent composition should be at least 0.2 of the hydrophobic powder to 1 part of the polyester resin.

In addition, in Test Examples 18 to 36 using the polyester resins of Test Examples 3 to 14, in which the results of the adhesion test described above were good, the water repellency after the peel test was also good, except for Test Example 22. rice field. This result is considered to be because the polyester resin was able to leave the hydrophobic silica on the substrate even after the tape was peeled off. In Test Example 22, it is considered that the polyester resin could not suppress the peeling of the hydrophobic silica due to the low relative viscosity of the polyester resin. From this, it is considered that the highly adhesive polyester resin of the present disclosure having a relative viscosity value of 1.33 or more can be suitably applied to the water repellent composition of the present disclosure.

When comparing Test Examples 16 to 21 using the polyester resin of Test Example 3 with Test Examples 23 to 36 using the polyester resins of Test Examples 4 to 14, Test Examples 23 to 36 are more water repellent after peeling as a whole. the results were good. In the polyester resins of Test Examples 4 to 14, the second aromatic polycarboxylic acid component contained a tetrabutylphosphonium 5-sulfoisophthalate component. It is believed that this phosphonium component suppressed the pseudo-crosslinking caused by the sodium 5-sulfoisophthalate component and was able to increase the strength of the polyester resin, so that Test Examples 23 to 36 had higher water repellency after peeling.

The water repellent compositions according to Test Examples 18-36 did not contain a volatile oily solvent. Therefore, it is possible to ensure the safety of workers during preparation and application of the water repellent composition. In addition, explosion-proof equipment becomes unnecessary, and costs related to safety can be reduced. Moreover, since no volatile oily solvent is used, waste liquid treatment can be facilitated. Furthermore, the water repellent composition of the present disclosure can also coat an oil-soluble substrate with a water repellent film.

All of the water-repellent articles produced in Test Examples 18 to 36 had flexibility similar to that of the polyester film substrate. As shown in Test Examples 3-5 and 7-14, the polyester resins of the present disclosure have high flexibility. This allows the water repellent composition of the present disclosure to be applied to substrates with high flexibility. That is, an article having a water-repellent coating formed by the water-repellent composition of the present disclosure can maintain the flexibility of the substrate itself. In addition, when the base material has porosity and air permeability, the article having the water repellent coating formed by the water repellent composition of the present disclosure can also maintain the porosity and air permeability.

[Test Examples 37-39]
A water repellency test and a water repellency test after peeling were conducted by changing the coating amount of the water repellent composition on the substrate. Fabricated in Test Example 33 so that the densities of the water-repellent coating made of polyester resin and hydrophobic silica after drying are 1.2 g/m ² , 2.5 g/m ² , and 5.0 g/m ^{2 ,} respectively. A water repellent agent composition is applied to a polyester film substrate, and a No. 3, No. 6, and no. It was applied using a No. 12 bar coater and dried to produce a substrate coated with a water-repellent coating having a uniform thickness (corresponding to the water-repellent article of the present disclosure). The prepared water-repellent article was subjected to a water-repellency test and a water-repellency test after peeling in the same manner as in Test Examples 15-36. The visible light transmittance of the water-repellent article was measured by UV-Vis (UVmini-1240 manufactured by Shimadzu Corporation) using air as a reference (100%) for the visible light transmittance. Table 6 shows the test results.

In Test Examples 37 to 39, high water repellency could be obtained. From this, it is considered that sufficient water repellency can be obtained even if the density of the water repellent film is lower than that of Test Example 37.

It was observed that the water repellency after the tape was peeled off tended to be higher when the coating amount of the water repellent composition was larger, that is, when the water repellent film density was higher. However, even in Test Example 37 in which the water-repellent film density was low, sufficient water repellency was confirmed even after the tape was peeled off.

In Test Examples 37 to 39, high transparency could be obtained even when a thick water-repellent film was formed. From this, it was found that the water repellent composition of the present disclosure can also be applied when transparency is required for water repellent articles.

[Test Examples 40 to 47]
In the water-repellent articles according to Test Examples 15 to 39, a polyester base material was used to form a water-repellent film. Therefore, in Test Examples 40 to 43, water repellent articles having base materials other than polyester base materials were produced and tested for water repellency. In Test Examples 44 to 47, the same test as in Test Examples 40 to 43 was performed on a commercially available water repellent agent containing silica, and the water repellent composition of the present disclosure was compared with water repellency and water repellency after peeling. .

In Test Examples 15 to 39, each substrate of glass, stainless steel, paper, and wood was tested using a bar coater (No. 6) so that the water-repellent film density was 2.5 g/m ² . The water repellent composition according to Example 33 was uniformly applied and dried to form a water repellent film on each substrate. In Test Examples 44 to 47, a water repellent agent was uniformly sprayed on each substrate of glass, stainless steel, paper, and wood according to the application of a spray-type commercially available water repellent agent, and each substrate was coated with a water repellent agent. A water-repellent film was formed. The test methods for water repellency and water repellency after peeling are the same as in Test Examples 15-36. Table 7 shows the test results.

The commercially available water repellent agents in Test Examples 44 to 47 could not provide water repellency to paper substrates. On the other hand, according to the water repellent compositions of the present disclosure in Test Examples 40 to 43, high water repellency could be obtained for all substrates. From this, it was found that the polyester resin of the present disclosure is capable of adhering hydrophobic powder to various substrates. It was found that the water repellent composition of the present disclosure can impart water repellency to various substrates.

In Test Examples 44, 45 and 47, the water repellency was lost when the tape was peeled off. On the other hand, in Test Examples 40 to 43, sufficient water repellency could be confirmed even after the tape was peeled off. From this, it was found that the polyester resin of the present disclosure can strongly adhere the hydrophobic powder to various substrates. It has been found that the water repellent composition of the present disclosure can impart durable water repellency to various substrates. That is, it was found that the water repellent article of the present disclosure can maintain water repellency for a long period of time.

The polyester resin, the water repellent composition, the water repellent article, and the method for producing these of the present disclosure are described based on the above embodiments and examples, but are not limited to the above embodiments and examples. , Within the scope of the present invention and based on the basic technical idea of the present invention, including various modifications, changes and improvements to each disclosed element (including elements described in claims, specifications and drawings) be able to. Moreover, various combinations, replacements, or selections of each disclosed element are possible within the scope of the claims of the present invention.

Further subjects, objects and modes (including modifications) of the present invention will be made clear from the entire disclosure of the present invention including claims.

Any numerical range recited herein should be construed as specifically recited herein for any number or range within that range, even if not otherwise stated.

The polyester resins of the present disclosure can also be applied to adhesive applications other than adhesion between particles and substrates. The polyester resin of the present disclosure can be applied to water-containing compositions (aqueous compositions) and emulsified compositions.

The water repellent composition of the present disclosure can be applied as long as it can be applied.

REFERENCE SIGNS LIST 1 substrate 2 polyester resin 3 hydrophobic powder 10 water-repellent article

Claims (17)

A polyester resin for attaching fine particles to a substrate,
The polyester resin contains a polymer of (A) an acid component and (B) an alcohol component,
The (A) component is, with respect to the total amount of the (A) component,
65 mol % to 92 mol % of (A1) a first aromatic polycarboxylic acid component containing a terephthalic acid component;
8 mol% to 20 mol% of (A2) a second aromatic polycarboxylic acid component,
The (A2) component contains a sodium 5-sulfoisophthalate component and a tetrabutylphosphonium 5-sulfoisophthalate component,
The component (B) is, with respect to the total amount of the component (B),
50 mol% to 90 mol% of an ethylene glycol component;
10 mol % to 40 mol % of a neopentyl glycol component,
A polyester resin having a relative viscosity value of 1.33 or greater. The (A) component is, with respect to the total amount of the (A) component,
further comprising 2 mol% to 15 mol% of (A3) an aliphatic polycarboxylic acid component,
The portion other than the carboxy group in the component (A3) has 2 to 8 carbon atoms,
The polyester resin according to claim 1, wherein the content of component (A1) is 65 mol% to 90 mol% of the total amount of component (A). 3. The polyester resin according to claim 2, wherein the (A3) component contains at least one of a succinic acid component and an adipic acid component. The (A2) component is, with respect to the total amount of the (A) component,
8 mol% to 19.5 mol% of a sodium 5-sulfoisophthalate component ;
0.5 mol % to 5 mol % of the tetrabutylphosphonium 5-sulfoisophthalate component . The component (B) is, with respect to the total amount of the component (B),
further comprising a diethylene glycol component of 3 mol% to 30 mol%;
The polyester resin according to any one of claims 1 to 4 , wherein the content of the ethylene glycol component is 50 mol% to 87 mol% with respect to the total amount of the component (B). 3% by mass or more of the polyester resin according to any one of claims 1 to 5 ,
a hydrophobic powder;
an aqueous solvent;
A water repellent composition, wherein a mass ratio of the polyester resin to the hydrophobic powder is 3.5 or less with respect to 1 part of the polyester resin. The water repellent composition according to claim 6 , wherein the content of the polyester resin is 10% by mass or less with respect to the mass of the water repellent composition. 8. The water repellent composition according to claim 6 , wherein the content of said hydrophobic powder is 0.5% by mass to 10% by mass with respect to the mass of the water repellent composition. The water repellent composition according to any one of claims 6 to 8 , wherein the hydrophobic powder is silica powder having an average primary particle size of 5 nm to 100 nm. The water repellent composition according to any one of claims 6 to 9 , wherein the aqueous solvent contains at least one of water and lower alcohol. The aqueous solvent is, with respect to the weight of the water repellent composition,
30% to 80% by weight of water;
The water repellent composition according to claim 10 , comprising 10% by mass to 55% by mass of a lower alcohol. The lower alcohol is methanol, ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, 1,2-propanediol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, glycerin , diethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monotertiary butyl ether, 3-methoxy-3-methylbutanol, Claim 10 or 11 , comprising at least one selected from 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether propionate, diethylene glycol monobutyl ether, and 1,5-pentanediol. water repellent composition. 13. The water repellent composition according to any one of claims 6 to 12 , wherein the surfactant content is 1% by mass or less. The water repellent composition according to any one of claims 6 to 13 , wherein the content of the volatile oily component is 5% by mass or less based on the mass of the water repellent composition. a substrate;
The polyester resin according to any one of claims 1 to 5 , which is arranged on at least a part of the base material; and
a hydrophobic powder adhered to the substrate by the polyester resin, at least a portion of which is exposed from the polyester resin. The water-repellent article according to claim 15 , wherein the total mass of the polyester resin and the hydrophobic powder in the area where the polyester resin and the hydrophobic powder are arranged is 0.1 g to 10 g per 1 m ² of substrate area. . 17. A water repellent article according to claim 15 or 16 , having at least one of flexibility and breathability.

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