WO2019188412A1

WO2019188412A1 - Primer composition, functional member, and method for producing functional member

Info

Publication number: WO2019188412A1
Application number: PCT/JP2019/010836
Authority: WO
Inventors: 足立　憲一; 承士奥村; 渡辺　陽一
Original assignee: 株式会社Ｌｉｘｉｌ
Priority date: 2018-03-29
Filing date: 2019-03-15
Publication date: 2019-10-03
Also published as: JP2021120421A

Abstract

A primer composition containing (A) an alkoxysilane having a specific structure, (B) one or more types of aminoalkylalkoxysilane selected from compounds represented by general formula (II-1) and general formula (II-2), and (C) an organic solvent. (In formula (II-1) and formula (II-2), R³ and R⁴ each independently represent a C1 or C2 alkyl group, x is an integer of 1-6, y is an integer of 1-10, n is an integer of 0-10, z is an integer of 1-10, and w is an integer of 1-10.)

Description

Primer composition, functional member and method for producing functional member

The present invention relates to a primer composition, a functional member, and a method for producing the functional member.
This application claims priority based on Japanese Patent Application No. 2018-065924 for which it applied to Japan on March 29, 2018, and uses the content here.

Surface modification for imparting various functions such as hydrophilicity and antibacterial properties to the surface of resin products installed in water-based spaces with facilities that use water, such as toilets and washstands Processing is in progress. One such surface modification process is a process of providing a functional layer that imparts functionality to the surface of a resin product. As a raw material for the functional layer, a silane coupling agent into which functional groups having various functionalities are introduced is used. In the process of providing a functional layer, a process of providing a primer layer between the surface of the resin product and the functional layer may be performed in order to improve the adhesion between the resin product and the functional layer. The primer layer is formed from a primer composition.

For example, Patent Document 1 is formed from a primer composition containing an overcoat layer (functional layer) formed from a hydrophilic silane coupling agent and an alkoxysilane having a specific structure on a substrate. A hydrophilic member having an undercoat layer (primer layer) has been proposed. In the hydrophilic member of Patent Document 1, the adhesion between the base material and the functional layer is enhanced by providing a primer layer on the surface of the base material.

Japanese Patent No. 512496

In order to further improve the hydrophilicity of the hydrophilic member of Patent Document 1, it is necessary to introduce more silane coupling agent having hydrophilicity.
However, the amount of silane coupling agent introduced into the functional layer formed on the hydrophilic member of Patent Document 1 is not sufficient.

The present invention has been made in view of such problems, and a primer composition, a functional member, and a method for producing a functional member that can introduce more silane coupling agents into the functional layer of the functional member. With the goal.

In order to achieve the above object, the present invention employs the following means.
One embodiment of the present invention includes one or more alkoxysilanes (A) selected from a compound represented by the following general formula (I-1) and a compound represented by the following general formula (I-2); Contains one or more aminoalkylalkoxysilanes (B) selected from a compound represented by the formula (II-1) and a compound represented by the following general formula (II-2), and an organic solvent (C) The primer composition.

In formula (I-1), each R ¹ independently represents an alkyl group having 1 to 4 carbon atoms. In formula (I-2), each R ² independently represents an alkyl group having 1 to 4 carbon atoms. m is 0 to 1000.

In formula (II-1), each R ³ independently represents an alkyl group having 1 or 2 carbon atoms. x is an integer of 1 to 6, y is an integer of 1 to 10, and n is an integer of 0 to 10. In formula (II-2), R ⁴ each independently represents an alkyl group having 1 or 2 carbon atoms. z is an integer of 1 to 10, and w is an integer of 1 to 10.

According to such a configuration, more silanol groups can be formed on the surface of the primer layer, which is a cured product of the primer composition. As a result, bonding with a larger number of silane coupling agents becomes possible.

One aspect of the present invention is a functional member comprising a resin base material, a primer layer located on one surface of the resin base material, and a functional layer located on the surface of the primer layer, the primer The layer is a functional member that is a cured product of the primer composition.

According to such a configuration, more silane coupling agents can be introduced into the functional layer, and a functional member having higher functionality can be provided.

One embodiment of the present invention may be a functional member in which the functional layer is a hydrophilic layer having hydrophilicity.

According to such a configuration, a silane coupling agent having more hydrophilicity can be introduced into the functional layer, and a functional member (hydrophilic member) having a hydrophilic layer having higher hydrophilicity can be provided.

One embodiment of the present invention is a method for producing a functional member, which includes a step of applying and curing the primer composition on one surface of a resin base material.

According to such a configuration, a primer layer capable of introducing more silane coupling agent into the functional layer can be formed. As a result, a functional member that is more excellent in functionality can be manufactured.

According to the primer composition of the present invention, more silane coupling agent can be introduced into the functional layer of the functional member.

It is sectional drawing which shows an example of the functional member which concerns on one Embodiment of this invention.

Hereinafter, an embodiment of the present invention will be described with reference to FIG.
A functional member 100 shown in FIG. 1 includes a primer layer 20 and a functional layer 30 on one surface of a resin base material 10. That is, the functional member 100 includes the resin base material 10, the primer layer 20, and the functional layer 30 in this order.

The thickness T ₁₀₀ of the functional member 100 is not particularly limited, but is preferably 0.001 to 500 mm, more preferably 0.001 to 300 mm, and still more preferably 0.001 to 200 mm. When the thickness T ₁₀₀ is equal to or greater than the lower limit, the strength of the functional member 100 is easily increased. When the thickness T ₁₀₀ is equal to or less than the above upper limit, the functional member 100 can be reduced in weight and easy to handle.
The thickness T ₁₀₀ of the functional member 100 can be measured using a caliper, for example.

As the resin base material 10, a general-purpose plastic material or an engineering plastic material can be used. Examples of the general-purpose plastic material include acrylonitrile-butadiene-styrene (ABS) resin, vinyl chloride resin, polystyrene (PS), polyethylene terephthalate (PET), and unsaturated polyester (UP) resin. Examples of the engineering plastic material include polycarbonate (PC), nylon resin, polyphenylene ether (PPE) and the like. The resin substrate 10 is preferably an ABS resin, a vinyl chloride resin, PET, PC, or UP resin from the viewpoint of excellent heat resistance.
As the resin base material 10, a resin in which a filler such as glass fiber, calcium carbonate, aluminum hydroxide, aluminum oxide, silica or the like is blended may be used.

The thickness _{T 10} of the resin substrate 10 is not particularly limited, for example, preferably 0.001 ~ 500 mm, more preferably 0.001 ~ 300 mm, more preferably 0.001 ~ 200 mm. If the thickness T ₁₀ is not less than the above lower limit, the strength of the functional member 100 is easily increased. If the thickness T ₁₀ is less than the above upper limit, can the functional member 100 to the light, it becomes easy to handle.
The thickness T ₁₀ of the resin substrate 10, for example, can be measured using calipers.

The primer layer 20 is a cured product of the primer composition according to the present invention. In the present specification, the cured product refers to one in which at least one selected from hydrolyzable alkoxysilanes and hydrolyzed polycondensates thereof has been insoluble and infusible by polycondensation or crosslinking with heat, a catalyst or the like.
The primer composition according to the present invention contains an alkoxysilane (A), an aminoalkylalkoxysilane (B), and an organic solvent (C).

The alkoxysilane (A) is at least one selected from a compound represented by the following general formula (I-1) and a compound represented by the following general formula (I-2).

Examples of the compound represented by the formula (I-1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Of the compounds represented by the formula (I-1), tetramethoxysilane and tetraethoxysilane are preferable from the viewpoint of easy dehydration condensation.

Examples of the compound represented by formula (I-2) include compounds in which R ² is a methyl group and m is 0 to 1000, R ² is an ethyl group and m is 0 to 1000, and R ² is a butyl group. Examples include compounds having m of 0 to 1000.
M in the compound represented by the formula (I-2) represents a degree of polymerization and is 0 to 1000, preferably 10 to 80, and more preferably 30 to 50. When the degree of polymerization m is equal to or higher than the lower limit, more silanol groups are easily formed on the surface of the primer layer 20. It is easy to melt | dissolve in an organic solvent (C) as the polymerization degree m is below the said upper limit. The compound represented by the formula (I-2) is a polymer obtained by dehydration condensation between two or more molecules of tetraalkoxysilane. When the degree of polymerization m is 0, the compound represented by the formula (I-2) is a tetraalkoxysilane dimer obtained by dehydration condensation of two tetraalkoxysilane molecules.
The degree of polymerization m can be controlled by the concentration of tetraalkoxysilane, the temperature during dehydration condensation, and the like.

As the compound represented by the formula (I-2), a tetraalkoxysilane represented by the formula (I-1) may be polymerized by dehydration condensation, or a commercially available product may be used. Examples of commercially available compounds represented by the formula (I-2) include methyl silicate oligomers MS51 and MS56 manufactured by Mitsubishi Chemical Corporation.

The content of the alkoxysilane (A) is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0% with respect to the total mass of the primer composition. More preferably, 3% by mass. It is easy to introduce more silane coupling agents into the functional layer 30 when the content of the alkoxysilane (A) is not less than the above lower limit. When the content of the alkoxysilane (A) is equal to or lower than the above upper limit value, it is easy to suppress the appearance change when the primer composition is applied to the resin substrate 10.

The amount of silicon atoms derived from the alkoxysilane (A) is preferably 1.0 to 60 μmol / g, more preferably 1.9 to 30 μmol / g, and more preferably 2.8 to 20 μmol / g with respect to 1 g of the primer composition. g is more preferable. It is easy to introduce more silane coupling agents into the functional layer 30 when the amount of silicon atoms derived from the alkoxysilane (A) is not less than the above lower limit. If the amount of silicon atoms derived from the alkoxysilane (A) is less than or equal to the above upper limit, it is easy to suppress changes in appearance when the primer composition is applied to the resin substrate 10.
The amount of silicon atoms derived from alkoxysilane (A) can be determined by elemental analysis of alkoxysilane (A).

The aminoalkylalkoxysilane (B) is at least one selected from a compound represented by the following general formula (II-1) and a compound represented by the following general formula (II-2).

In the formula (II-1), x is an integer of 1 to 6, preferably 2 to 6. When x is within the above numerical range, hydrolysis of alkoxysilane (A) and the polycondensation reaction subsequent to hydrolysis are likely to be promoted.
In the formula (II-1), y is an integer of 1 to 10, and preferably 2 to 3. When y is within the above numerical range, the dehydration condensation reaction of alkoxysilane (A) is likely to be promoted.
In the formula (II-1), n is an integer of 0 to 10, preferably 1 or 2. When n is within the above numerical range, the dehydration condensation reaction of alkoxysilane (A) is likely to be promoted.

Examples of the compound represented by the formula (II-1) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2 -Aminoethyl) aminopropyltriethoxysilane, 3- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (6-aminohexyl) aminopropyltriethoxysilane, trimethoxysilylpropyldiethylenetriamine and the like. As the compound represented by the formula (II-1), 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (6-amino) is preferable from the viewpoint that adhesion with a silane coupling agent is more easily exhibited. Hexyl) aminopropyltrimethoxysilane is preferred.

In the formula (II-2), z is an integer of 1 to 10, and preferably 2 to 4. When z is within the above numerical range, the dehydration condensation reaction of alkoxysilane (A) is likely to be promoted.
In the formula (II-2), w is an integer of 1 to 10, and preferably 2 to 4. When w is within the above numerical range, the dehydration condensation reaction of alkoxysilane (A) is likely to be promoted.

Examples of the compound represented by the formula (II-2) include bis (3- (triethoxysilyl) propyl) amine, bis (3- (trimethoxysilyl) propyl) amine, and the like. The compound represented by the formula (II-2) is preferably bis (3- (trimethoxysilyl) propyl) amine from the viewpoint of easy hydrolysis.

The content of the aminoalkylalkoxysilane (B) is preferably 0.0002 to 1% by mass, more preferably 0.002 to 0.6% by mass, and 0.01 to 0% with respect to the total mass of the primer composition. More preferably, 3% by mass. When the content of the aminoalkylalkoxysilane (B) is not less than the above lower limit, it is easy to introduce more silane coupling agents into the functional layer 30. When the content of the aminoalkylalkoxysilane (B) is not more than the above upper limit, it is easy to suppress changes in appearance when the primer composition is applied to the resin substrate 10.

The amount of silicon atoms derived from the aminoalkylalkoxysilane (B) is preferably 0.01 to 60 μmol / g, more preferably 0.1 to 30 μmol / g, more preferably 0.5 to 15 μmol / g is more preferable. When the amount of silicon atoms derived from the aminoalkylalkoxysilane (B) is equal to or greater than the lower limit, more silane coupling agents can be easily introduced into the functional layer 30. When the amount of silicon atoms derived from the aminoalkylalkoxysilane (B) is less than or equal to the above upper limit, it is easy to suppress changes in appearance when the primer composition is applied to the resin substrate 10.
The amount of silicon atoms derived from the aminoalkylalkoxysilane (B) can be determined in the same manner as the amount of silicon atoms derived from the alkoxysilane (A).

The ratio of the amount of silicon atoms derived from aminoalkylalkoxysilane (B) to the amount of silicon atoms derived from alkoxysilane (A) in the primer composition (hereinafter also referred to as B / A ratio). 0.005 to 1, preferably 0.015 to 0.5, and more preferably 0.05 to 0.2. When the B / A ratio is equal to or higher than the lower limit, it is easy to introduce more silane coupling agents into the functional layer 30. When the B / A ratio is less than or equal to the above upper limit value, it is easy to suppress changes in appearance when the primer composition is applied to the resin substrate 10.

The total of the content of alkoxysilane (A) and the content of aminoalkylalkoxysilane (B) (hereinafter also referred to as A + B amount) is 0.01 to 5 mass relative to the total mass of the primer composition. % Is preferable, 0.02 to 3% by mass is more preferable, and 0.04 to 1.2% by mass is further preferable. When the amount of A + B is not less than the above lower limit value, it is easy to introduce more silane coupling agents into the functional layer 30. When the A + B amount is not more than the above upper limit value, it is easy to suppress changes in appearance when the primer composition is applied to the resin base material 10.

The organic solvent (C) is not particularly limited as long as it dissolves or disperses alkoxysilane (A) and aminoalkylalkoxysilane (B) to form a primer composition. Examples of the organic solvent (C) include alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol (IPA), 1-butanol, 2-butanol, 2-methyl-2-propanol, acetone, methyl ethyl ketone, Ketone solvents such as diethyl ketone, chlorine solvents such as dichloromethane and trichloromethane, aromatic solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, diethyl ether, tetrahydrofuran and dioxane Examples include ether solvents, glycol ether solvents such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether. Among these organic solvents, alcohol solvents and ketone solvents that easily dissolve alkoxysilane (A) and aminoalkylalkoxysilane (B) are preferable, alcohol solvents are more preferable, ethanol, 2-propanol, and 1-butanol. Is more preferable.
An organic solvent (C) may be used individually by 1 type, and may use 2 or more types together.

The content of the organic solvent (C) is preferably 95 to 99.99% by mass, more preferably 97 to 99.98% by mass, and more preferably 98.8 to 99.96% by mass with respect to the total mass of the primer composition. Is more preferable. When the content of the organic solvent (C) is equal to or higher than the lower limit, it is easy to suppress a change in appearance when the primer composition is applied to the resin base material 10. When the content of the organic solvent (C) is not more than the above upper limit value, it is easy to introduce more silane coupling agents into the functional layer 30.

The primer composition which concerns on this invention may contain the arbitrary components except an alkoxysilane (A), an aminoalkyl alkoxysilane (B), and an organic solvent (C) as needed. Examples of the optional component include a surface conditioner and water.
When the primer composition according to the present invention contains an optional component, the content of the optional component is preferably 0.00001 to 1% by mass with respect to the total mass of the primer composition.

The thickness _{T 20} of the primer layer 20 is not particularly limited, for example, preferably 0.001 ~ 2 [mu] m, more preferably 0.002 ~ 0.6 .mu.m, more preferably 0.005 ~ 0.2 [mu] m. When the thickness T ₂₀ is equal to or greater than the lower limit, the functional layer 30 can be easily formed uniformly on the surface of the primer layer 20. When the thickness T ₂₀ is equal to or less than the above upper limit value, it is easy to improve the adhesion between the one surface of the resin base material 10 and the primer layer 20.
The thickness T ₂₀ of the primer layer 20 can be measured using X-ray photoelectron spectroscopy apparatus.

The functional layer 30 is a layer that can impart various functionalities to the resin base material 10.
Examples of the functional layer 30 include a hydrophilic layer having hydrophilicity, a water repellent layer having water repellency, and an antibacterial layer having antibacterial properties. As the functional layer 30, a hydrophilic layer having hydrophilicity is preferable from the viewpoint of use in a water space having equipment using water.

The functional layer 30 contains a silane coupling agent. In this specification, the silane coupling agent is a compound composed of an organic substance and silicon, and refers to a compound having two or more different reactive groups in the molecule. One of the reactive groups is a reactive group that chemically bonds to an inorganic material, and the other is a reactive group that chemically bonds to an organic material. By using a silane coupling agent, it is possible to bind an organic material and an inorganic material that are usually very difficult to bond.

Examples of silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrimethoxysilane, and 3-glycid. Xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3 -(Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 4-vinylphenyltrimethoxy Lan, 3- (4-vinylphenyl) propyltrimethoxysilane, 4-vinylphenylmethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3- Examples include mercaptopropylmethyldiethoxysilane and partial hydrolysates thereof. As the silane coupling agent, methoxysilane or ethoxysilane is preferable in terms of operability and ease of distilling off by-products.
These silane coupling agents may be used alone or in combination of two or more.

The functional layer 30 may contain a compound capable of imparting various functionalities to the resin base material 10 in addition to the silane coupling agent. Various functionalities include hydrophilicity, water repellency, antibacterial properties and the like.
Examples of the compound capable of imparting hydrophilicity include the hydrophilic compounds described in Japanese Patent Application Laid-Open No. 2016-020461. Examples of the hydrophilic compound include sodium Nt-butylacrylamide sulfonate, sodium vinyl sulfonate, 2-sodium sulfoethyl methacrylate, sodium allyl sulfonate, sodium p-styrene sulfonate, 3-mercapto-1-propane. Examples thereof include sodium sulfonate.
Examples of the compound capable of imparting water repellency include silane coupling agents such as KBM-1703 (manufactured by Shin-Etsu Chemical Co., Ltd.).
Examples of the compound capable of imparting antibacterial properties include silane coupling agents such as AEM-5700 (manufactured by AEGIS ENVIRONMENTS).

The thickness _{T 30} of the functional layer 30 is not particularly limited, for example, preferably 0.0004 ~ 1 [mu] m, more preferably from 0.0008 ~ 0.5 [mu] m, more preferably 0.001 ~ 0.3 [mu] m. When the thickness T ₃₀ is equal to or greater than the lower limit, it is easy to impart sufficient functionality to the resin base material 10. If the thickness T ₃₀ is less than the above upper limit, it is easy to improve the adhesion between the primer layer 20.
The thickness T ₃₀ of the functional layer 30 can be measured using X-ray photoelectron spectroscopy apparatus.

The amount of silane coupling agent introduced is proportional to the amount of silanol groups in the primer layer 20. The amount of the silanol group in the primer layer 20 can be confirmed by the peak of the siloxane bond in infrared spectroscopy. The larger the siloxane bond peak, the greater the amount of silanol groups in the primer layer 20. The peak of siloxane bond in infrared spectroscopy can be seen around 1050 cm ⁻¹ .
The amount of silanol groups in the primer layer 20 can also be confirmed by the peak of methylene groups in infrared spectroscopy. The smaller the methylene group peak, the fewer alkoxy groups remaining in the primer layer 20, and the more silanol groups. The peak of the methylene group in infrared spectroscopy is seen around 2950 cm ⁻¹ .

As the functional member 100, a hydrophilic member having hydrophilicity is preferable from the viewpoint of use in a water space having equipment that uses water.
When the functional member 100 is a hydrophilic member, as an index for evaluating the hydrophilicity of the functional member 100, a method of dropping a water droplet on the surface of the functional member 100 and measuring the contact angle of water can be given. As an apparatus for measuring the contact angle of water, for example, a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) is used. The dropping solution is distilled water, the dropping amount is 1.0 μL, and the contact angle can be calculated by the θ / 2 method (A half-angle method).
The contact angle of water is defined from 0 ° to 180 °, and the smaller the angle, the more hydrophilic. When the functional member 100 is a hydrophilic member, the contact angle of water is preferably 0 to 60 °, more preferably 0 to 40 °, and further preferably 0 to 30 °. The functional member 100 is excellent in hydrophilicity as the contact angle of water is below the upper limit. Although the lower limit of the contact angle of water is preferably as small as possible, it is substantially about 5 °.

Applications for which hydrophilic members can be applied include, for example, housing equipment, toilet bowls, bathtubs, washstands, kitchenware, windows, doors, floors, desks, vehicle bodies, solar panels, walls, displays, signs, touch panels, etc. Can be mentioned.

When the functional member 100 is a water repellent member, the index for evaluating the water repellency of the functional member 100 includes a method of measuring the contact angle of water as in the index for evaluating the hydrophilicity of the functional member 100. It is done.
When the functional member 100 is a water repellent member, the contact angle of water is preferably 60 to 180 °, more preferably 70 to 180 °, and even more preferably 80 to 180 °. The functional member 100 is excellent in water repellency that the contact angle of water is more than the said lower limit. The upper limit of the water contact angle is preferably as large as possible, but is substantially about 150 °.

Applications for which the water-repellent member can be applied include, for example, housing equipment, toilet bowls, bathtubs, sinks, kitchenware, windows, doors, floors, desks, vehicle bodies, solar panels, walls, displays, signs, touch panels, etc. Can be mentioned.

When the functional member 100 is an antibacterial member, the antibacterial evaluation of the functional member 100 is performed according to the antibacterial test method described in JIS Z2801. The antibacterial property of the functional member 100 is determined based on the antibacterial activity value specified in JIS Z2801. If the antibacterial activity value is 2.0 or more, the functional member 100 is excellent in antibacterial properties.

Examples of applications to which the antibacterial member can be applied include housing equipment, toilet bowls, bathtubs, washstands, kitchenware, windows, doors, floors, desks, walls, handles, touch panels, toys, and medical equipment.

The shape of the functional member 100 is not particularly limited, and may be, for example, a rectangular shape in plan view or an elliptical shape in plan view.

The method for producing a functional member according to the present invention includes a step of forming a primer layer and a step of forming a functional layer. By the method for producing a functional member according to the present invention, a functional member including a primer layer located on one surface of a resin base material and a functional layer located on the surface of the primer layer is obtained.
The step of forming the primer layer is a step of applying and curing the primer composition according to the present invention on one surface of the resin base material.

The primer composition according to the present invention is prepared by dissolving an alkoxysilane (A) and an aminoalkylalkoxysilane (B) and, if necessary, a surface conditioner (optional component) in an organic solvent (C) and then stirring. can get. The method for stirring the primer composition is not particularly limited, and the primer composition can be stirred by a conventional method.
The method for applying the primer composition to one surface of the resin substrate 10 is not particularly limited. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film applicator method, screen printing. Methods such as coating, bar coating, brush coating, and sponge coating are applicable.
The application amount of the primer composition is not particularly limited, and for example, 1 to 50 g is preferable and 5 to 20 g is more preferable with respect to the resin base material 10 having a size of 100 cm × 100 cm. When the coating amount of the primer composition is within the above numerical range, the thickness T ₂₀ of the primer layer 20 is easily set to 0.001 to 2 μm.

It is preferable to degrease one surface of the resin base material 10 in advance before applying the primer composition. By degreasing one surface of the resin base material 10 in advance, the adhesion between the resin base material 10 and the primer layer 20 can be further enhanced. For degreasing, an organic solvent such as acetone, ethanol, 2-propanol or the like can be used.

The method of curing the primer composition is not particularly limited, and examples thereof include a method of curing by heating at an arbitrary temperature. The temperature for curing the primer composition can be appropriately determined in consideration of the composition of the primer composition, the coating amount, and the curing time. The temperature for curing the primer composition is preferably, for example, 15 to 120 ° C., more preferably 30 to 100 ° C. When the temperature for curing the primer composition is at least the above lower limit, the dehydration condensation reaction of alkoxysilane (A) and aminoalkylalkoxysilane (B) tends to proceed. When the temperature at which the primer composition is cured is equal to or lower than the upper limit, it is easy to suppress the deterioration of the resin base material 10.

The step of forming the functional layer is a step of applying and curing a compound capable of imparting functionality including a silane coupling agent (hereinafter, also referred to as “functionality imparting compound”) on the surface of the primer layer.
The method for applying the functionality-imparting compound to the surface of the primer layer 20 is not particularly limited, and a method similar to the method for applying the primer composition to one surface of the resin substrate 10 can be applied.
The application amount of the functional compound is, for example, preferably 2 to 50 g, more preferably 5 to 20 g with respect to the area of the primer layer 20 of 100 cm × 100 cm. When the coating amount of the functional compound is within the above numerical range, the thickness T ₃₀ of the functional layer 30 is easily adjusted to 0.0004 to 1 μm.

The method of curing the functional compound is not particularly limited, and examples thereof include a method of curing by heating at an arbitrary temperature. The temperature for curing the functionality-imparting compound can be appropriately determined in consideration of the composition of the functionality-imparting compound, the coating amount, and the curing time. The temperature for curing the functional compound is preferably, for example, 15 to 120 ° C., more preferably 30 to 100 ° C. When the temperature for curing the functional compound is equal to or higher than the above lower limit, the dehydration condensation reaction of the silane coupling agent easily proceeds. When the temperature at which the functionality-imparting compound is cured is equal to or lower than the above upper limit value, it is easy to suppress deterioration of the resin substrate 10.

Examples of the function-imparting compound include a hydrophilicity-imparting compound, a water repellency-imparting compound, and an antibacterial property-imparting compound. The functionality-imparting compound only needs to contain a silane coupling agent, and may be the silane coupling agent itself. Examples of the hydrophilicity-imparting compound include a mixture of the above-described hydrophilic compound and a silane coupling agent. Examples of the water repellency imparting compound include the above-mentioned KBM-1703 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the antibacterial property-imparting compound include AEM-5700 (manufactured by AEGISENVIRONMENTS) described above.

The primer layer 20 is formed on one surface of the resin base material 10 by the step of forming the primer layer. Through the step of forming the functional layer, the functional member 100 in which the functional layer 30 is formed on the surface of the primer layer 20 is obtained.

As mentioned above, although embodiment of this invention was described in detail with reference to drawings, this invention is not limited to said embodiment, In the range which does not deviate from the meaning of this invention, it can change suitably. . Moreover, it is possible to replace the constituent elements in the above-described embodiments with known constituent elements as appropriate.

In the above-described embodiment, the primer layer 20 is provided on one surface of the resin base material 10. However, the present invention is not limited to this, and the primer layer 20 may be provided on both surfaces of the resin base material 10.
In the above-described embodiment, the functional layer 30 is provided on one surface of the resin base material 10. However, the present invention is not limited to this, and the functional layer 30 may be provided on both surfaces of the resin base material 10.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
The alkoxysilane (A) and aminoalkylalkoxysilane (B) used in this Example are as shown in [Use Raw Materials] below.

[Raw materials]
≪Alkoxysilane (A) ≫
MS56: Methyl silicate oligomer MS56, R ² in formula (I-2) is a methyl group, m is 0 to 98, manufactured by Mitsubishi Chemical Corporation.
MS51: Methyl silicate oligomer MS51, R ² in the formula (I-2) is a methyl group, m is 0 to 98, manufactured by Mitsubishi Chemical Corporation.
TEOS: Tetraethoxysilane, R ¹ in formula (I-1) is an ethyl group, manufactured by Tokyo Chemical Industry Co., Ltd.
TBOS: tetrabutoxysilane, R ¹ in formula (I-1) is an n-butoxy group, manufactured by Tokyo Chemical Industry Co., Ltd.

≪Aminoalkylalkoxysilane (B) ≫
KBM603: 3- (2-aminoethyl) aminopropyltrimethoxysilane, R ³ in formula (II-1) is a methyl group, x is 2, y is 3, n is 1, manufactured by Shin-Etsu Chemical Co., Ltd.
KBE603: 3- (2-aminoethyl) aminopropyltriethoxysilane, R ³ in the formula (II-1) is an ethyl group, x is 2, y is 3, n is 1, manufactured by Shin-Etsu Chemical Co., Ltd.
KBM903: 3-aminopropyltrimethoxysilane, R ³ in formula (II-1) is a methyl group, y is 3, n is 0, manufactured by Shin-Etsu Chemical Co., Ltd.
KBE903: 3-aminopropyltriethoxysilane, R ³ in formula (II-1) is an ethyl group, y is 3, n is 0, manufactured by Shin-Etsu Chemical Co., Ltd.
Bis (3- (triethoxysilyl) propyl) amine: R ⁴ in the formula (II-2) is an ethyl group, z is 3, w is 3, Fluorochem Ltd. Made.

[Example 1]
≪Preparation of primer composition≫
As an alkoxysilane (A), MS56 is converted to a silicon atom substance amount of 5.6 μmol / g, and as an aminoalkylalkoxysilane (B), KBM-603 is converted to a silicon atom substance amount of 1.0 μmol / g, The resultant was mixed with 20 g of 1-butanol and dissolved by stirring for 5 minutes to obtain a primer composition containing 99.5% by mass of 1-butanol. In Tables 1 to 4, “-” indicates that the corresponding component is not added.

≪Formation of primer layer≫
UP was used as a resin substrate, and the surface of the UP was wiped with acetone and then degreased by wiping with 2-propanol (IPA).
Subsequently, 0.1 g of the primer composition was applied to one surface of the degreased 5 cm × 10 cm resin base material by a bar coater method. Thereafter, the primer composition was cured by leaving it at a temperature of 60 ° C. for 30 minutes using an electric oven to form a primer layer having a thickness of 0.1 μm.

≪Formation of hydrophilic layer≫
After 1 part by mass of 3-acryloxypropyltrimethoxysilane and 98 parts by mass of 1-methoxy-2-propanol were stirred and mixed at room temperature, 1 part by weight of a 70% by mass aqueous isethionic acid solution was added, and the mixture was further stirred for 5 minutes. Decomposition was carried out (preparation of solution 1). After the obtained solution 1 was applied on the surface of the primer layer with a waste cloth, it was heated at 100 ° C. for 10 seconds to volatilize the solvent and the like, and the silanol groups generated from 3-acryloxypropyltrimethoxysilane and the surface of the primer layer A silanol group was subjected to a dehydration condensation reaction to obtain a base material on which a layer serving as a base of the hydrophilic layer was formed.
Next, 27.5 parts by mass of ion-exchanged water and 10 parts by mass of urea were mixed and stirred until urea was dissolved. Then, Nt-butylacrylamide sodium sulfonate (50% by mass aqueous solution, number average) was used as the hydrophilic compound. 50.0 parts by mass of molecular weight 229), IRGACURE (registered trademark) 500 (mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) manufactured by BASF, and 10.0 parts by mass of isopropyl alcohol were added. Stir until a clear homogeneous solution is obtained (Preparation of Solution 2). 20 g of the obtained solution 2 was applied to the substrate with a waste cloth and irradiated with a metal halide lamp at an intensity of 30 mW per cm ² for 10 seconds, and then the substrate was washed with water to provide a hydrophilic layer having a thickness of 3 nm. A 5 mm thick hydrophilic member was prepared. In addition, what combined the solution 1 and the solution 2 is made into a hydrophilic provision compound. The numerical value in the table is the mass of the hydrophilic compound (sodium Nt-butylacrylamide sulfonate).

<Measurement of contact angle>
Water droplets were dropped on the surface of the obtained hydrophilic member, and the contact angle was measured. A contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) was used as a device for measuring the contact angle. The dropping solution was distilled water, the dropping amount was 1.0 μL, and the contact angle was calculated by the θ / 2 method. The smaller the contact angle, the better the hydrophilicity.

[Examples 2 to 8]
A hydrophilic member was prepared in the same manner as in Example 1 except that the resin base material shown in Table 1 was used, and the contact angle was measured.

[Examples 9 to 21]
A hydrophilic member was prepared in the same manner as in Example 1 except that the primer compositions shown in Tables 2 to 3 were used, and the contact angle was measured.

[Example 22]
≪Formation of primer layer≫
A primer layer was formed in the same manner as in Example 1.

≪Formation of water repellent layer≫
After 1 part by weight of KBM-1703 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 98 parts by weight of 1-methoxy-2-propanol were stirred and mixed at room temperature, 1 part by weight of a 70% by weight aqueous solution of isethionic acid was added for another 5 minutes. Stirring and hydrolysis were carried out (preparation of solution 3 (water repellency imparting compound)). 10 g of the solution 3 was applied to the surface of the primer layer with a waste cloth and dried at room temperature (25 ° C.) to prepare a water repellent member having a thickness of 5 mm and a water repellent layer having a thickness of 1 nm. For the evaluation of water repellency, the contact angle was measured in the same manner as the evaluation of hydrophilicity.

[Example 23]
≪Formation of antibacterial layer≫
0.75 g of trimesic acid was dissolved in 230 mL of ion-exchanged water while stirring at 60 ° C., and allowed to cool to room temperature (25 ° C.). Thus, Solution 4 was prepared. 12 g of AEM5700 (manufactured by AEGISENVIRONMENTS) was mixed with 76.6 mL of ion-exchanged water and stirred for 7 minutes to obtain Solution 5. These solutions 4 and 5 were mixed to obtain a solution 6 (antibacterial property imparting compound). The resin base material on which the primer layer is formed in the solution 6 is dipped for 30 minutes and then taken out and cured at a temperature of 90 ° C. for 60 minutes using an electric oven to obtain an antibacterial member having a thickness of 5 mm and having an antibacterial layer having a thickness of 3 nm. Produced.
The antibacterial evaluation was performed according to the antibacterial test method described in JIS Z2801.

[Reference Examples 1 to 3]
A hydrophilic member was prepared in the same manner as in Example 1 except that the resin base material shown in Table 4 was used, and the contact angle was measured.

[Comparative Examples 1 and 2]
A hydrophilic member was prepared in the same manner as in Example 1 except that UP was used as the resin base material and a primer composition not containing aminoalkylalkoxysilane (B) was used, and the contact angle was measured.

[Comparative Examples 3 to 9]
Using the resin base materials shown in Tables 4 to 5, the contact angle was measured in the same manner as in Example 1.

As shown in Tables 1 to 5, it was found that Examples 1 to 21 to which the present invention was applied were excellent in hydrophilicity. It was found that Example 22 to which the present invention was applied was excellent in water repellency. It was found that Example 23 to which the present invention was applied was excellent in antibacterial properties.
Thus, it turned out that various functionality can be provided to a resin base material by using the primer composition concerning the present invention.
On the other hand, Comparative Examples 1 and 2 which do not contain aminoalkylalkoxysilane (B) have a larger contact angle than Examples 1 and 9 which contain aminoalkylalkoxysilane (B), and are able to impart sufficient hydrophilicity. I found that there was no. It was found that Comparative Examples 3 to 9 which did not impart hydrophilicity had a large contact angle.

It was found that according to the primer composition of the present invention, various functionalities can be imparted to the resin base material. This is considered to be because more silane coupling agent can be introduced into the functional layer of the functional member according to the primer composition of the present invention.

The primer composition according to the present invention can be used particularly suitably for resin products installed in a water space having facilities that use water, such as toilet bowls and washstands.

DESCRIPTION OF SYMBOLS 10 Resin base material 20 Primer layer 30 Functional layer 100 Functional member

Claims

One or more alkoxysilanes (A) selected from a compound represented by the following general formula (I-1) and a compound represented by the following general formula (I-2);
One or more aminoalkylalkoxysilanes (B) selected from a compound represented by the following general formula (II-1) and a compound represented by the following general formula (II-2);
A primer composition containing an organic solvent (C).

(In Formula (I-1), each R 1 independently represents an alkyl group having 1 to 4 carbon atoms. In Formula (I-2), each R 2 independently represents an alkyl group having 1 to 4 carbon atoms. M is 0 to 1000.)

(In Formula (II-1), each R 3 independently represents an alkyl group having 1 or 2 carbon atoms, x is an integer of 1 to 6, y is an integer of 1 to 10, and n is 0 to An integer of 10. In formula (II-2), R 4 each independently represents an alkyl group having 1 or 2 carbon atoms, z is an integer of 1 to 10, and w is an integer of 1 to 10. is there.)
A functional member comprising a resin base material, a primer layer located on one surface of the resin base material, and a functional layer located on the surface of the primer layer,
The said primer layer is a functional member which is a hardened | cured material of the primer composition of Claim 1.
The functional member according to claim 2, wherein the functional layer is a hydrophilic layer having hydrophilicity.
The manufacturing method of a functional member which has the process of apply | coating the primer composition of Claim 1 to one side of a resin base material, and making it harden | cure.