JP2018122543A - Antifouling coat structure and method for forming the same, measurement apparatus, and ophthalmologic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling coat structure which can be applied not only to metal but also to a resin surface, and has high durability.SOLUTION: An antifouling coat structure has a resin layer having an etched surface, a glass-like coat layer provided on the resin layer, and a perfluoroalkylsilane layer provided on the glass-like coat layer. In the antifouling coat structure, tetraalkoxysilane and a solvent containing an etching component of a resin are applied onto the resin surface, alkoxysilane is hydrolyzed to form the glass-like coat layer, the solvent containing the perfluoroalkyltrialkoxysilane is applied to the glass-like coat layer, and the perfluoroalkyltrialkoxysilane is hydrolyzed to form a perfluoroalkylsilane layer. The method can also apply the tetraalkoxysilane, the perfluoroalkyltrialkoxysilane and the solvent containing the etching component of the resin as a single liquid.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a technique for improving the antifouling property of an article surface made of resin, and more particularly, to an antifouling coat structure and a method for forming the same, a surveying instrument having an antifouling coat structure in a housing, and an ophthalmic instrument.

  Surveying equipment such as rotating lasers used at construction sites and pipe lasers used at construction sites where sewer pipes are installed are used in harsh outdoor environments, so in addition to rainwater, soil, cement, filth, etc. There was a problem that dirt adhered to the surveying instrument. In addition, ophthalmic equipment such as an optometry apparatus used in ophthalmology or a spectacle store has a problem that an eye drop adheres or dirt such as sebum adheres when a patient is examined.

  When these stains are wiped from the equipment casing, the stains themselves are difficult to remove, and in the case of cement, scratches due to particles may remain, or stains of components contained in the stain may remain. .

  As an antifouling coat for preventing such dirt from being attached and facilitating the removal when it is attached, a monomolecular repellent that has been conventionally sold by Daikin, Shin-Etsu Chemical, Dow Corning, 3M, etc. Water / oil repellent coating materials are known (see, for example, Patent Documents 1 and 2).

  Since this monomolecular water / oil repellent coating material has an ether bond in the molecule of the active ingredient, the molecules of the long chain structure are oriented in a specific direction to form a monomolecular film on the surface of the article. This monomolecular film containing an ether bond is known to improve the antifouling property of the water / oil repellent coating layer when applied to an article because of its high water repellency angle.

  As a fluorine-based water- and oil-repellent coat having no ether bond, for example, a fluoroalkylsilane compound is known. Since this water / oil repellent coat layer has a fluorine functional group, it is difficult for dirt to adhere to it, and the stability of the molecules constituting the water / oil repellent coat layer is higher than that having an ether bond. , Membrane durability is high.

  On the other hand, in Patent Document 3, in a mold that requires releasability of an object to be transferred, which is the same property as antifouling property, the mold surface is activated by irradiating excimer ultraviolet light, thereby releasing the release layer. Techniques for forming the are disclosed. According to this technique, the adhesion between the mold and the release layer is improved, and the durability of the release layer is improved.

Japanese Patent No. 3275402 Japanese Patent No. 3433024 Japanese Patent No. 40202094

  However, conventional monomolecular water / oil repellent coats as shown in Patent Documents 1 and 2 do not have any physical and chemical bonds with the base material, and are simply applied. Therefore, there is a problem that the adhesion is low and the water / oil repellent coat is easily peeled off.

  Further, in the technique described in Patent Document 3, since the surface of the mold is modified by excimer laser light to activate the surface, the mold surface and the mold release are performed rather than the case of simply applying without modification. Although the adhesion with the film is somewhat improved, the problem that it is insufficient and the mold release durability is inferior has not been solved. In addition, this surface activation technique is applied in the case of metal and is not compatible with surveying instruments and ophthalmic instruments whose casing is made of a resin such as ABS.

  The present invention has been made in view of the above situation, and can be applied not only to a metal as a base material but also to a resin surface. An object is to provide a surveying instrument and an ophthalmic instrument having a coat structure.

  The invention according to claim 1, which solves the above problem, has an antifouling coating structure, and is provided in a resin layer whose surface is etched, a glass-like coat layer provided on the resin layer, and a glass-like coat layer. And a perfluoroalkylsilane layer.

  The invention according to claim 2 is a method for forming the antifouling coating structure, wherein a solvent containing tetraalkoxysilane and a resin etching component is applied to the resin surface, and the alkoxysilane is hydrolyzed. A glass-like coat layer is formed, a solvent containing perfluoroalkyltrialkoxysilane is applied to the glass-like coat layer, and the perfluoroalkyltrialkoxysilane is hydrolyzed to form a perfluoroalkylsilane layer. To do.

  The invention according to claim 3 is a method for forming the antifouling coating structure, wherein a solvent containing tetraalkoxysilane, perfluoroalkyltrialkoxysilane, and an etching component of the resin is applied to the resin surface, A glass-like coat layer and a perfluoroalkylsilane layer are formed by hydrolyzing alkoxysilane and perfluoroalkyltrialkoxysilane.

  According to the present invention, the resin surface is dissolved by the etching component contained in the solvent, fine irregularities are formed on the surface of the resin layer, and the glass-like coat layer comprising silicon and oxygen is formed by condensation polymerization of tetraalkoxysilane. Once formed, this layer is physically bonded through the irregularities of the resin layer.

  Further, the perfluoroalkyltrialkoxysilane undergoes condensation polymerization to form a perfluoroalkylsilane layer, and also condenses with the OH group of the glass-like coat layer to form a siloxane bond.

  Thus, since the resin layer and the glass-like coat layer are physically bonded and the glass-like coat layer and the perfluoroalkylsilane layer are chemically bonded, the adhesion between the three is greatly improved. Thereby, the antifouling property of the perfluoroalkyl group protruding to the outermost surface can be exhibited for a long period of time, and the antifouling property of the resin casing used in a harsh environment can be improved.

It is sectional drawing which shows typically the formation process of the antifouling coating structure which concerns on 1st Embodiment of this invention. It is sectional drawing which shows typically the formation process of the antifouling coat structure concerning 2nd Embodiment of this invention. It is a schematic diagram which shows the chemical state in the glass-like coat layer lamination process of 1st Embodiment. It is a schematic diagram which shows the chemical state in the glass-like coat layer lamination process of 1st Embodiment. It is a schematic diagram which shows the chemical state in the perfluoroalkyl silane layer lamination process after the glass-like coat layer lamination | stacking of 1st Embodiment. It is a schematic diagram which shows the chemical state after the perfluoroalkylsilane layer lamination | stacking of 1st Embodiment. It is a schematic diagram which shows the chemical state in the one liquid lamination process of the antifouling layer which has the glass-like coat part + perfluoroalkylsilane part of 2nd Embodiment. It is a schematic diagram which shows the chemical state after 1 liquid lamination | stacking of the antifouling layer which has a glass-like coat part + perfluoroalkylsilane part of 2nd Embodiment. It is a photograph which shows the test result of an Example and a comparative example.

Hereinafter, the present invention will be described in more detail.
1. First embodiment: two-component lamination of a glass-like coat layer and a perfluoroalkylsilane layer (1-1. Configuration)
FIG. 1 shows an antifouling coating structure 1 according to the first embodiment of the present invention. Moreover, the chemical state at the time of forming each layer of the antifouling coating structure 1 in FIGS.

  In FIG. 1 (d), reference numeral 10 denotes a base material made of a resin such as ABS. The present invention is mainly applied to the housing of surveying instruments and ophthalmic instruments, but is limited to these. Not.

  A glass-like coat layer 11 mainly composed of silicon and oxygen is laminated on a resin base material 10 having a nano-order fine unevenness formed on the surface by etching. The glass-like coat layer 11 enters a fine recess on the surface of the resin base material 10 and is physically bonded by an anchor effect.

  A perfluoroalkylsilane layer 12 is laminated on the glass-like coat layer 11. In both layers, the OH group present on the surface of the glass-like coat layer 11 and the OH group present on the surface (lower side) of the perfluoroalkylsilane layer 12 are condensed and chemically formed by a siloxane bond (Si—O—Si). It is in a state of being coupled to.

  As shown in FIG. 6, perfluoroalkyl groups are oriented on the surface (upper side) of the perfluoroalkylsilane layer 12 to prevent the adhesion of dirt, scratches during wiping, and the generation of spots due to dirt components. Demonstrate dirtiness.

(1-2. Formation process)
Next, the formation process of the antifouling coating structure of the first embodiment will be described. As shown to Fig.1 (a), the resin-made base materials 10 which are housings | casings, such as a surveying instrument and an ophthalmic apparatus, are prepared. The surface of the resin substrate 10 may have irregularities such as embossing and embossing from the beginning, or may be smooth. In the figure, a smooth state is illustrated.

  Subsequently, as shown in FIG. 1B, tetraalkoxysilane, a component capable of dissolving the resin base material 10, and other additives as necessary are added to the surface of the resin base material 10. A solvent dissolved in a soluble solvent (hereinafter sometimes abbreviated as a glass-like coating agent) is applied.

  When the glass-like coating agent is applied and then allowed to stand, a component (etching component) capable of dissolving the resin base material 10 dissolved in the solvent erodes the surface of the resin base material 10 and is shown in FIG. In this manner, nano-order fine irregularities are formed on the surface of the resin base material 10. At the same time, as shown in FIGS. 3 and 4, the alkoxy groups of the tetraalkoxysilane are hydrolyzed by moisture in the atmosphere and condensed to form a glass-like network. As shown in FIG. 1C and FIG. 5, the glass-like coat layer 11 is cured in a state where it enters a fine concave portion of the resin base material 10 and is physically bonded by an anchor effect. On the surface of the glass-like coat layer 11, many OH groups generated by hydrolysis of the alkoxy groups of tetraalkoxysilane protrude from the surface.

  Next, as shown in FIG. 5, on the surface of the glass-like coat layer 11, a perfluoroalkyltrialkoxysilane and, if necessary, other additives are dissolved in a solvent capable of dissolving them ( Hereinafter, it may be abbreviated as a perfluoroalkylsilane agent).

  When left to stand after application of the perfluoroalkylsilane agent, as shown in FIG. 6, the alkoxy groups of the perfluoroalkyltrialkoxysilane are hydrolyzed by moisture in the atmosphere, and the perfluoroalkyltrialkoxysilanes undergo condensation polymerization. At the same time, the OH group protruding from the glass-like coat layer 11 is condensed to form a siloxane bond. Thus, the glass-like coat layer 11 and the perfluoroalkylsilane layer 12 are chemically bonded.

(1-3. Effect)
According to the first embodiment, since a solvent containing a tetraalkoxysilane and a solvent containing a resin etching component is applied to the resin surface, the resin surface is dissolved by the etching component, and nano-order fine irregularities Is formed on the surface of the resin layer, and the tetraalkoxysilane is hydrolyzed and condensation-polymerized to form a glass-like coat layer composed of silicon and oxygen. This layer is physically formed through the fine irregularities of the resin layer. Glued.

  Further, in the first embodiment, since the solvent containing perfluoroalkyltrialkoxysilane is applied to the glass-like coat layer, the perfluoroalkyltrialkoxysilane is hydrolyzed and subjected to condensation polymerization, so that perfluoroalkylsilane is obtained. In addition to forming a layer, it also condenses with the OH groups of the glass-like coat layer to form siloxane bonds.

  In this way, the resin layer and the glass-like coat layer are physically bonded by the anchor effect, and the glass-like coat layer and the perfluoroalkylsilane layer are chemically bonded by a siloxane bond. There is an effect that it is remarkably improved.

2. Second embodiment: One-component lamination of antifouling layer (glass-like coat portion and perfluoroalkylsilane portion) (2-1. Configuration)
FIG. 2 shows an antifouling coating structure 2 according to the second embodiment of the present invention. Moreover, the chemical state at the time of forming each layer of the antifouling coating structure 2 is shown in FIGS. In FIG. 2C, reference numeral 20 denotes the same resin base material as in the first embodiment.

  A portion corresponding to the glass-like coat layer 11 and a portion corresponding to the perfluoroalkylsilane layer 12 in the first embodiment are 1 on the resin base material 20 that has been etched to form nano-order fine irregularities on the surface. The antifouling layer 21 formed inside the layer is laminated. The antifouling layer 21 is formed by one-component lamination and does not have a clear interface, but is separated into a glass-like coat portion and a perfluoroalkylsilane portion. The glass-like coat portion existing below the antifouling layer 21 enters a fine recess on the surface of the resin base material 20 and is physically bonded by the anchor effect.

  In the antifouling layer 21, the OH group derived from the glass-like coat portion and the OH group derived from the perfluoroalkylsilane portion are condensed and chemically bonded by a siloxane bond (Si—O—Si).

  As shown in FIG. 8, a perfluoroalkyl group is oriented on the surface (upper side) of the antifouling layer 21 and is antifouling against the adhesion of dirt, scratches when wiping off, and the generation of spots due to dirt components. Demonstrate.

(2-2. Formation process)
Next, the formation process of the antifouling coating structure of the second embodiment will be described. As shown in FIG. 2A, a resin-made base material 20 that is a housing of a surveying instrument, an ophthalmic instrument, or the like is prepared. The surface of the resin base material 20 shows a smooth state.

  Subsequently, as shown in FIG. 2 (b), tetraalkoxysilane, a component capable of dissolving the resin substrate 20, a perfluoroalkyltrialkoxysilane, and other materials as needed are formed on the surface of the resin substrate 10. And a solvent in which these are dissolved in a solvent capable of dissolving them (hereinafter sometimes referred to as a one-component antifouling coating agent).

  When the one-part antifouling coating agent is applied and left standing, a component (etching component) capable of dissolving the resin base material 20 dissolved in the solvent erodes the surface of the resin base material 20, and FIG. 2 (c) As shown in FIG. 2, nano-order fine irregularities are formed on the surface of the resin substrate 20.

  At this time, as shown in FIGS. 7 and 8, the alkoxy groups of the tetraalkoxysilane are hydrolyzed by moisture in the atmosphere and condensed to form a glass-like network, and at the same time, perfluoroalkyltrialkoxy. The alkoxy group of silane is hydrolyzed by moisture in the atmosphere, and the perfluoroalkyltrialkoxysilane is condensed and polymerized, and the OH group derived from the glass-like coat portion and the OH group derived from the perfluoroalkylsilane portion are condensed. Form a siloxane bond.

  Thus, the antifouling layer 21 is formed in a state in which the glass-like coat portion and the perfluoroalkylsilane portion are separated in the antifouling layer 21 and are chemically bonded to each other by a siloxane bond. As shown in FIG. 2C and FIG. 8, the glass-like coat portion of the antifouling layer 21 is cured in a state where it enters a fine concave portion of the resin base material 20 and is physically bonded by an anchor effect.

  As a mechanism for separating the glass-like coat portion and the perfluoroalkylsilane portion vertically within the single antifouling layer 21, the solubility parameter changes as the solvent evaporates, and one component that cannot be completely dissolved is given priority. This is explained by the fact that the surface energy of the perfluoroalkyl group is low and the surface energy (upper side) is preferentially precipitated.

(2-3. Effects)
According to the present invention, since the tetraalkoxysilane, the resin etching component, and the solvent containing perfluoroalkyltrialkoxysilane are applied to the resin surface in the second embodiment, the resin surface is dissolved by the etching component. Nano-order fine irregularities are formed on the surface of the resin layer, and the tetraalkoxysilane is hydrolyzed and condensation polymerized to form a glass-like coat portion composed of silicon and oxygen. Are physically bonded through uneven surfaces. At the same time, the perfluoroalkyltrialkoxysilane is hydrolyzed and subjected to condensation polymerization to form a perfluoroalkylsilane portion, and at the same time, condensed with the OH group of the glass-like coat portion to form a siloxane bond.

  In this way, the resin layer and the antifouling layer are physically bonded, and the glass-like coat portion and the perfluoroalkylsilane portion are chemically bonded within the antifouling layer, so that the adhesion between the two layers is remarkably increased. improves. Thereby, the antifouling property of the perfluoroalkyl group protruding from the outermost surface can be exhibited for a long period of time, and the antifouling property of the surveying instrument and the ophthalmic device used in a harsh environment can be improved.

(3. Other)
The present invention is particularly effective for a resin that has few OH groups on the surface, unlike metal and glass, is difficult to activate, and it is difficult to perform antifouling coating directly. Examples of such resins include vinyl resins (polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol), polystyrene resins (polystyrene, styrene / acrylonitrile copolymer, styrene / butadiene / acrylonitrile (ABS) copolymer, polyethylene ( High density / medium density / low density), ethylene / vinyl acetate copolymer), polypropylene resin, polyacetal resin, polymethyl methacrylate resin, urethane resin, silicone resin, COP, COC, etc., surveying equipment, ophthalmic equipment ABS, which is frequently used in the housings of other measuring devices and medical devices, is particularly preferable.

  The glass-like coat layer in the first embodiment of the present invention is preferably formed to a thickness of several hundred μm or less. The reason is that cracks tend to occur as the thickness increases.

  The perfluoroalkylsilane layer in the first embodiment of the present invention is preferably several nm to several tens of nm.

  The antifouling layer in the second embodiment of the present invention is applied at once by blending both materials so as to be a glass-like coat layer + perfluoroalkylsilane layer having a thickness in the same range as in the first embodiment. It is preferable to do.

  As the alkoxysilane contained in the glass-like coating agent and the one-part antifouling coating agent of the present invention, a siloxane bond network is formed in all bonding directions of silicon, so that a 4,3,2 functional material is selected. Tetra / tri / dimethoxysilane, tetra / tri / diethoxysilane, and tetra / tri / dipropoxysilane are preferred. The concentration range in the solvent is 50 to 99% in the first embodiment and 80 to 99% in the second embodiment.

  The perfluoroalkyltrialkoxysilane contained in the perfluoroalkylsilane agent and the one-part antifouling coating agent of the present invention has a perfluoroalkyl group that exhibits antifouling performance in one bonding direction of silicon, and the rest In order to form a network of siloxane bonds in the three bond directions, it is required to have three alkoxy groups.

As the functional group of the fluorocarbon, a perfluoroalkyl group C (CF ₃ ) ₃ (CF ₂ ) _n group or a perfluoropolyether group C (CF ₃ ) ₃ (CF ₂ O) _n (CF ₂ ) ₂ is preferable. .

  The functional alkoxy group is preferably a methoxy group, an ethoxy group, or a propoxy group.

  In the present invention, a glass-like coating agent, a perfluoroalkylsilane agent, and an antifouling coating agent can be applied by a known coating method, dipping method, vacuum deposition method, sputtering method, chemical vapor deposition method, etc. The wet method is preferable from the viewpoint of necessity and cost of applying to the entire casing of the device.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
Since some products of surveying instruments are used at the site where concrete is applied, the concrete adheres to the casing and becomes dirty. In order to reproduce the situation, raw concrete was applied to the surface of the surveying instrument housing of the example and the comparative example, dried, and then the concrete was peeled off, and the appearance after peeling was observed. In the examples, the antifouling coating structure of the first embodiment of the present invention was adopted on the surface of the surveying instrument housing made of ABS resin. In the comparative example, the surface remains uncoated ABS resin.

  When the antifouling coating of the example was applied, the concrete peeled off when the main body was vibrated and dropped. In this way, the deposits were easy to remove, and no trace was left as shown in FIG. On the other hand, in the comparative example, the concrete was strongly adhered and had to be peeled off with a finger. Moreover, as shown in FIG.9 (b), the concrete peeling trace remained on the surface.

  The antifouling performance of surveying instruments and ophthalmic instruments used in harsh environments can be improved by demonstrating the antifouling property of perfluoroalkyl groups protruding from the outermost surface of the antifouling coating layer over a long period of time. it can.

1: Antifouling coating structure 10: Resin base material (resin layer)
11: Glass-like coating layer 12: Perfluoroalkylsilane layer 2: Antifouling coating structure 20: Resin substrate (resin layer)
21: Antifouling layer formed by one-component lamination (glass-like coat portion + perfluoroalkylsilane portion)

Claims (5)

A resin layer whose surface is etched;
A glass-like coat layer provided on the resin layer;
And a perfluoroalkylsilane layer provided on the glass-like coat layer. A method for forming an antifouling coating structure according to claim 1,
A solvent containing tetraalkoxysilane and the etching component of the resin is applied to the resin surface,
Hydrolyzing the alkoxysilane to form the glass-like coat layer;
A solvent containing perfluoroalkyltrialkoxysilane is applied to the glass-like coat layer,
A method for forming an antifouling coating structure, wherein the perfluoroalkyltrialkoxysilane is hydrolyzed to form a perfluoroalkylsilane layer. A method for forming an antifouling coating structure according to claim 1,
Applying a solvent containing tetraalkoxysilane, perfluoroalkyltrialkoxysilane, and an etching component of the resin to the resin surface,
A method for forming an antifouling coating structure, comprising hydrolyzing the alkoxysilane and the perfluoroalkyltrialkoxysilane to form the glass-like coat layer and the perfluoroalkylsilane layer.   A surveying instrument comprising the antifouling coating structure according to claim 1 on a resin casing surface.   An ophthalmic device comprising the antifouling coating structure according to claim 1 on the surface of a resin casing.

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