JP2013123677A - Method for producing surface-modified molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a surface-modified molding, in which efficient production can be achieved.SOLUTION: The method for producing the surface-modified molding includes a step of bringing a gas containing a vaporized silane coupling agent into contact with the surface of an untreated molding comprising a resin, an inorganic material or a combination thereof. The concentration of the silane coupling agent in the gas is 20-100% of the saturated concentration. The flow velocity of the gas flowing at 5 mm height from the surface of the untreated molding and in parallel with the surface of the untreated molding is ≥10 cm/sec.

Description

  The present invention relates to a method for producing a molded body having a modified surface.

  A plate material made of a resin or an inorganic material is excellent in properties such as gas barrier performance and transparency, and thus is used as a substrate in an optical device such as a display device or a lighting device. Furthermore, it is known that such a plate material can be subjected to surface modification treatment with a silane coupling agent to increase the bonding strength with other members (Patent Documents 1 to 3).

JP 2008-229413 A International Publication No. WO2007 / 119552 International Publication No. WO2011 / 010738

  In Patent Documents 1 to 3, the treatment with a silane coupling agent is performed by filling a sealed container, which has been reduced to atmospheric pressure or reduced pressure, with the vapor of the silane coupling agent and placing the sample therein. However, such a process has a problem that it takes time to complete the process and it is difficult to improve the manufacturing efficiency. Such a problem is particularly remarkable in a manufacturing process that requires high efficiency, such as manufacturing in which a large number of materials or large-sized materials are processed at high speed.

  Accordingly, an object of the present invention is to provide a method for producing a surface-modified molded body that enables efficient production.

As a result of studying to solve the above-mentioned problems, the present inventors have determined that the concentration of the silane coupling agent in the gas to be treated with the silane coupling agent is within a predetermined range, and that the flow rate of the gas is at least a predetermined level. And found that this problem can be solved. The present invention has been completed based on such findings.
That is, according to the present invention, the following [1] to [5] are provided.

[1] A method for producing a surface-modified molded article,
A step of bringing a gas containing a vaporized silane coupling agent into contact with the surface of a pre-processed molded body made of a resin, an inorganic material, or a combination thereof;
The concentration of the silane coupling agent in the gas is 20% or more and 100% or less of the saturation concentration,
The manufacturing method in which the component parallel to the surface of the pre-processed molded body of the gas flow velocity at a height of 5 mm from the surface of the pre-processed molded body is 10 cm / sec or more in the contacting step.
[2] The manufacturing method according to [1], wherein in the contacting step, the gas further contains water vapor.
[3] The production method according to [1] or [2], further including a step of exposing the molded body before treatment to water vapor prior to the contacting step.
[4] The production method according to any one of [1] to [3], wherein the molded body before treatment includes a resin, and the resin is a resin including an alicyclic structure-containing polymer.
[5] The surface treatment method according to any one of [1] to [4], wherein the molded body before treatment includes an inorganic material, and the inorganic material includes glass.

  According to the production method of the present invention, it is possible to efficiently produce a surface-modified molded body that has been subjected to a surface treatment that provides high peel strength.

FIG. 1 is a side view of a pre-processed molded body in a process of contacting a processing gas. FIG. 2 is a longitudinal sectional view showing an example of a specific aspect of the step of bringing the processing gas into contact. FIG. 3 is a longitudinal sectional view showing another example of a specific aspect of the step of bringing the processing gas into contact. FIG. 4 is a side view showing still another example of a specific aspect of the step of bringing the processing gas into contact. FIG. 5 is a side view showing still another example of a specific mode of the step of bringing the processing gas into contact.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples, and the claims of the present invention and equivalents thereof. Any change can be made without departing from the scope described above.

  The production method of the present invention is a method for producing a surface-modified molded body. In the present application, the surface-modified molded body is obtained by modifying the surface of the molded body. In the present application, a molded body before such a modification treatment is referred to as a “pre-treatment molded body”, and a molded body subjected to such a modification treatment is referred to as a “surface modified molded body”. Hereinafter, the term “molded body” is used as a generic term for these.

(Molded before treatment)
The molded body before processing usually has a plate shape having a front surface and a back surface of a flat surface or a curved surface. The “surface” of the molded body before processing, which is the target of the modification treatment, is a part or all of the outer surface of the molded body. The surface to be treated usually includes a part or all of one or both of the front surface and the back surface of the plate-shaped pre-processed molded body.

The pre-processed molded body is made of a resin, an inorganic material, or a combination thereof.
Examples of the resin include a resin containing an alicyclic structure-containing polymer; a vinyl alcohol resin such as polyvinyl alcohol; a chain polyolefin resin such as polyethylene and polypropylene; an aromatic vinyl polymer resin such as polystyrene; Polyamide resin; Polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate and polyarylate; Polyimide resin; Acrylic resin such as polymethyl methacrylate;
Among these, a resin containing a vinyl alcohol resin and an alicyclic structure-containing polymer is preferred, a resin containing an alicyclic structure-containing polymer is more preferred, and an alicyclic structure containing a tertiary carbon in the molecule A resin containing a polymer is particularly preferred.

  The alicyclic structure-containing polymer is a polymer containing a repeating unit having an alicyclic structure. Since the resin containing the alicyclic structure-containing polymer is excellent in transparency and emits less water and small organic molecules, the surface-modified molded product obtained by the production method of the present invention can be used as an optical material, precision It is particularly suitable for use in applications such as equipment materials.

  Specific examples of the alicyclic structure-containing polymer include norbornene polymers, monocyclic cycloalkene addition polymers, vinylcycloalkane polymers, and the like. One of these can be used alone or in combination of two or more.

  Examples of the alicyclic structure include monocycles and polycycles (condensed polycycles, bridged rings, combination polycycles thereof, and the like). The number of carbon atoms constituting the alicyclic structure is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15. When the carbon number of the alicyclic structure is within the above range, various properties such as mechanical strength, heat resistance and moldability are highly balanced, which is preferable.

  In the alicyclic structure-containing polymer, the proportion of the repeating unit having an alicyclic structure is usually 20 to 100% by weight, preferably 30 to 100% by weight. If the proportion of the repeating unit having an alicyclic structure is too small, the heat resistance may be inferior. Repeating units other than the repeating unit having an alicyclic structure are appropriately selected according to the purpose of use.

  The norbornene-based polymer is an addition polymer or ring-opening polymer of a monomer having a norbornene ring structure, or a hydride thereof. The addition polymer of a monocyclic cycloalkene is an addition polymer of a monocyclic cycloalkene monomer or an alicyclic conjugated diene monomer, or a hydride thereof. The polymer of vinylcycloalkane is a polymer of vinylcycloalkane or vinylcycloalkene, or a hydride thereof, or a hydride of an aromatic ring portion of an aromatic vinyl polymer. These alicyclic structure-containing polymers may be copolymers of the above monomers with other monomers that can be copolymerized.

  The alicyclic structure-containing polymer further has polar groups such as hydroxyl group, carboxyl group, alkoxyl group, epoxy group, glycidyl group, oxycarbonyl group, carbonyl group, amino group, ester group, and carboxylic anhydride group. However, those having no polar group are preferred.

  Among these alicyclic structure-containing polymers, it has a norbornene ring structure because it is excellent in moldability and has less autofluorescence, so it can be suitably used for applications such as fluorescence analysis, and has a small amount of elution. Monomer ring-opening polymers and hydrides thereof are preferred, and the effects of the monomer ring-opening polymer having a norbornene ring structure and a hydride thereof having a norbornene ring structure when plasma irradiation is performed. Is particularly preferred since it becomes higher.

  The glass transition temperature of the resin is not particularly limited, but is preferably 100 ° C. or higher, more preferably 130 ° C. or higher.

  The polymerization method for obtaining the alicyclic structure-containing polymer and the hydrogenation method performed as necessary are not particularly limited and can be performed according to a known method.

  The resin may contain various additives in addition to the main polymer. There is no special limitation as an additive, The additive of a normal resin can be used. For example, antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, ultraviolet absorbers, near infrared absorbers and other stabilizers; lubricants, plasticizers and other resin modifiers; dyes, pigments and other colorants; Antistatic agents; and the like. Any one of these additives may be used alone, or two or more thereof may be used in combination. The addition amount of these additives is appropriately selected within a range that does not impair the object of the present invention.

Examples of the inorganic material include glass, single crystal sapphire, quartz, calcium fluoride, barium fluoride, and magnesium fluoride. More specifically, examples of the glass include soda glass, lead glass, borosilicate glass, alkali-free glass, quartz glass, and chemically strengthened glass.
The molded body before treatment may be a single layer made of one type of resin or inorganic material, or may be a combination of two or more types of these. For example, it may have a plurality of layers. In this case, the materials (resin and / or inorganic material) constituting the plurality of layers may be the same or different.

  When processing the pre-processed molded body, the pre-processed molded body may be a composite material combined with a member other than the resin and the inorganic material. In this case, since the layer on the surface of the composite material is composed of the pre-process molded body, the pre-process molded body on the composite material can be used in the method of the present invention. For example, a composite member that includes a pre-processed molded body that is exposed to a front surface and is bonded to a member other than a resin and an inorganic material via the back surface is subjected to treatment with a silane coupling agent, and the composite member. The manufacturing method of the present invention can also be performed by processing the front surface.

(Processing gas)
The production method of the present invention includes a step of bringing a gas containing a vaporized silane coupling agent (hereinafter, sometimes referred to as “treatment gas”) into contact with the surface of the molded body before treatment.
Any known silane coupling agent can be used as the silane coupling agent.
As specific examples of the silane coupling agent,
Having vinyl groups such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane;
Having an epoxy group such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane;
having a styryl group such as p-styryltrimethoxysilane;
Those having a methacryloxy group such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxymethyldiethoxysilane, 3-methacryloxytriethoxysilane;
Having an acryloxy group such as 3-acryloxypropyltrimethoxysilane;
N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidenepropylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2 -Those having an amino group such as aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-6135, etc.);
Having a ureido bond such as 3-ureidopropyltriethoxysilane;
Containing halogen atoms such as 3-chloropropyltrimethoxysilane;
Those having a mercapto group such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane;
Having a sulfide bond such as bis (triethoxysilylpropyl) tetrasulfide;
Having an isocyanate group such as 3-isocyanatopropyltriethoxysilane;
Etc. One of these can be used alone, or two or more can be used in combination.

The processing gas can contain a carrier gas in addition to the silane coupling agent. As such a carrier gas, an inert gas such as nitrogen, helium, or argon can be used.
The concentration of the silane coupling agent in the processing gas is 20% or more of the saturation concentration, preferably 40% or more, more preferably 60% or more, and 100% or less, 95% or less. It is preferable that it is 90% or less. By setting the silane coupling agent concentration to 20% or more of the saturation concentration, an efficient modification treatment can be performed.

  The processing gas can further contain water vapor as required. By containing water vapor, a silane coupling treatment that provides high peel strength can be achieved more efficiently. The content ratio of water vapor in the processing gas can be 5% to 100% of the saturation concentration.

  The processing gas can further contain an optional gas component as required. Examples of such optional gas components include methanol and ethanol. The content ratio of an arbitrary gas component in the processing gas can be 0.1% to 10% of the saturation concentration.

(Process gas contact)
In the step of bringing the processing gas into contact with the pre-processed molded body, the flow rate of the processing gas at a height of 5 mm from the surface of the pre-processed molded body is parallel to the surface of the pre-processed molded body (surface to be processed). This component is 10 cm / sec or more, preferably 100 cm / sec or more, more preferably 500 cm / sec or more. By performing contact at such a speed, a silane coupling treatment that provides high peel strength can be efficiently achieved. On the other hand, the upper limit of the speed is not particularly limited, but may be 5000 cm / sec or less.

  A component of the flow rate of the processing gas parallel to the surface of the molded body before processing will be described with reference to FIG. FIG. 1 is a side view of a pre-processed molded body in a process of contacting a processing gas. In FIG. 1, the pre-processed molded body 11 has a surface 11S, and the surface 11S is processed with a processing gas. In this case, the speed of the processing gas on the surface 13 (shown by a broken line) at a height of 5 mm from the surface 11S (shown by an arrow h in FIG. 1) is examined.

In this example, when the wind direction of the processing gas at the point 14 on the surface 13 is parallel to the surface 13 as shown by the arrow A11 (that is, parallel to the surface 11S), “the processing gas flow velocity is processed. The “component parallel to the surface of the preform” is equal to the flow rate of the processing gas.
As another example, when the wind direction of the processing gas at the point 14 on the surface 13 forms an angle θ with the surface 13 as indicated by an arrow A12, “the flow velocity of the processing gas is parallel to the surface of the molded body before processing”. The “component” is obtained by an equation of v1 = v cos θ (where v is the flow velocity of the processing gas, and v1 is a component parallel to the surface of the pre-processed molded body at the flow velocity of the processing gas). The range of θ is preferably 60 ° to 90 °.

A specific mode of the step of bringing the processing gas into contact with the pre-processed molded body will be described with reference to FIGS.
In the example shown in FIG. 2, the container 21 has an introduction port 22 and a discharge port 23. On the inner bottom surface in the container 21, the pre-processed molded body 11 is placed with the surface 11S to be processed facing upward. The processing gas is introduced into the container 21 from the introduction port 22 as shown by an arrow A 21, flows through the container 21, and is discharged from the discharge port 23. The flow rate of the processing gas at a height of 5 mm from the surface 11S in the container 21 is monitored by the anemometer 24, and the speed of the processing gas introduced from the inlet 22 is adjusted so that the flow rate becomes a desired speed. Can do. Thereby, the processing gas can be brought into contact with the surface 11S of the molded body 11 before processing at a desired flow rate.

  In the example shown in FIG. 3, the container 31 includes a blower 33. The blower 33 can circulate the gas in the container 31 in the direction indicated by the arrow A31. By placing the device 32 for vaporizing the silane coupling agent in the container 33 and vaporizing the silane coupling agent, the processing gas can be circulated in the container 31 at a desired flow rate. The flow rate can be monitored with an anemometer (not shown) installed in the vicinity of the pre-processed compact as necessary. By placing the pre-process molded body 11 in such a container 31, the processing gas can be brought into contact with the surface 11S of the pre-process molded body 11 at a desired flow rate.

  In the example shown in FIG. 4, the processing gas is blown by the nozzle 41 onto the surface 11S of the pre-processed molded body 11, thereby flowing the gas as indicated by arrows A <b> 41 to A <b> 42. Moreover, in the example shown in FIG. 5, the gas for a process is sprayed on the surface 11S of the molded object 11 before a process with the shower head 51, and, thereby, the gas is flowed as shown by arrow A51-A54. Also according to such an aspect, the processing gas can be brought into contact with the surface 11S of the molded body 11 before processing at a desired flow rate.

(Preprocessing)
Prior to the step of bringing the processing gas into contact with the pre-process molded body, the pre-process molded body can be subjected to any pre-treatment. Examples of such pretreatment include plasma irradiation, excimer ultraviolet irradiation, corona discharge, and steam treatment. Since it is possible to perform surface treatment uniformly, plasma irradiation is preferable, and atmospheric pressure plasma irradiation is more preferable.

The atmospheric pressure plasma irradiation can be performed using, for example, an atmospheric pressure plasma surface treatment apparatus (product name “AP-T03-L”, manufactured by Sekisui Chemical Co., Ltd.).
The atmospheric pressure plasma irradiation is preferably performed in one or more gas atmospheres selected from hydrogen, helium, nitrogen, oxygen, and argon, and more preferably mixed with nitrogen and dry air or oxygen. The flow rate of nitrogen is preferably 50 to 150 NL / min, and the flow rate of dry air or oxygen is preferably 0.1 to 5 NL / min. The output of plasma irradiation is preferably 0.5 to 2 kW. The frequency of plasma irradiation is preferably a resonance frequency corresponding to the output, and specifically, a range of 10 to 100 KHz is preferable. The irradiation rate of plasma irradiation is preferably 1 to 100 cm / min. The distance between the plasma generation source and the surface to be processed is preferably between 1 and 10 mm.

  When plasma irradiation is performed under reduced pressure instead of normal pressure, plasma treatment is performed using a low pressure gas (such as argon gas, oxygen gas, nitrogen gas, or a mixed gas thereof) of 0.001 to 10 kPa (absolute pressure). It is preferable to carry out. As the low-pressure gas, it is particularly preferable to use a mixed gas of nitrogen and oxygen. The mixing ratio of nitrogen and oxygen is preferably 10: 1 to 1:10 by volume, and the flow rate of the mixed gas is preferably 0.1 to 10 NL / min. The output of plasma irradiation is preferably 50 to 500W.

  Excimer ultraviolet irradiation is preferably performed using an excimer ultraviolet lamp while flowing a mixed gas of nitrogen and dry air or oxygen. The oxygen concentration of the air-fuel mixture is usually 1 to 15%, preferably 3 to 5%. The flow rate of the gas mixture is preferably 3 to 7 liters / minute. The distance between the lamp and the surface to be treated is preferably 10 mm or less, and more preferably 1 to 5 mm. The intensity of irradiation is preferably 20 to 100 mW, more preferably 30 to 50 mW.

The corona discharge is preferably performed in a dry air atmosphere, and the flow rate of the dry air is preferably 10 to 100 NL / min. The output of the corona discharge is preferably 250 to 1000 W, and the discharge electric energy is preferably 20 to 550 W · min / m ² .

  The steam treatment is a treatment for exposing the molded body before treatment to water vapor. By performing such a treatment, moisture can be adhered to the surface of the pre-treated molded body. By adhering moisture in this manner, a silane coupling treatment that provides high peel strength can be achieved more efficiently. The steam treatment can be performed by bringing the pre-treatment shaped body into contact with steam generated by an ultrasonic humidifier, a steam humidifier or the like.

  In the case of performing steam treatment as pretreatment, such treatment is preferably performed immediately before the step of bringing the treatment gas into contact with the pre-treatment molded body. As a result, the pre-processed compact can be subjected to the contact step with an effective amount of moisture attached to the surface. Therefore, when performing both steam treatment and other treatments (plasma irradiation, excimer ultraviolet irradiation, and one or more treatments including corona discharge) as pretreatment, it is preferable to perform the steam treatment step later.

(Use of product)
The molded body processed by the step of bringing the processing gas into contact with the pre-processed molded body can be used as a surface-modified molded body as it is or after being subjected to any treatment such as heat treatment as necessary. The use of the surface-modified molded product obtained by the production method of the present invention is not particularly limited, but it can be used as a laminate by being bonded to another member. For example, a surface-modified molded body is obtained as a surface-modified glass substrate or a surface-modified resin film, and the surface treated with the silane coupling agent is pasted to the surface of another member treated with silane coupling. Thus, a laminate can be configured. Bonding can be performed, for example, by stacking the surface-modified molded body and another member, and thermocompression bonding using a laminator. The conditions for thermocompression bonding can be appropriately selected according to the material used, but the pressure can be 0.1 to 5 MPa, and the temperature can be 80 to 150 ° C.

  The use of the laminate including the surface-modified molded body is not particularly limited. It can be used as a layer having these functions or a composite having these functions.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to the Example shown below. In the following description of Examples, “%” and “parts” representing amounts are based on weight unless otherwise specified. Further, the operations described below were performed under normal temperature and normal pressure conditions unless otherwise specified.

<Example 1>
(1-1. Pretreatment of glass substrate)
A glass substrate (thickness 0.7 mm, manufactured by Corning, trade name “Eagle XG”) was cut into a square of 50 mm square, and then an atmospheric pressure plasma surface treatment device (product name “AP-T03-L”, Sekisui Chemical Co., Ltd.) was used to perform atmospheric pressure plasma irradiation at an output of 1.5 kW, a frequency of 25 kHz, a nitrogen gas flow rate of 50 L / min, and an irradiation rate of 30 cm / min, to obtain a pretreated glass substrate.

(1-2. Treatment of glass substrate with silane coupling agent)
3-aminopropyltrimethoxysilane (product name “KBM-903”, manufactured by Shin-Etsu Chemical Co., Ltd.) vaporized using a vaporizer (VU-550: manufactured by Lintec Corporation) and nitrogen were mixed to produce 3-aminopropyl. A processing gas 1 was generated in which the concentration of trimethoxysilane was 90% of the saturated concentration.
The processing gas 1 was introduced from the inlet 22 of the container 21 shown in FIG. 2 and discharged from the outlet 23 to circulate the container 21. In this state, the pre-treated glass substrate obtained in the step (1-1) is put in the container 21, and one surface of the glass substrate (in the figure, on the upper surface 11S of the pre-processed molded body 11). Silane coupling agent treatment was performed by bringing the treatment gas 1 into contact for a predetermined time to obtain a surface-modified glass substrate.
At the time of processing, the flow velocity of the processing gas 1 is set at 5 mm from the surface 11S of the substrate 11 by an anemometer 24 (manufactured by Tonic Co., Ltd .: pasting type wind speed air temperature probe QB-5, digital 1CH anemometer GeY-10DA). It was used to monitor and adjusted to 500 cm / sec. Moreover, the processing time set different time in each of many glass substrates. The processing time was appropriately set to 3 seconds, 5 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, and further thereafter increasing at 10-second intervals.

(1-3. Preparation of surface-modified resin film for evaluation)
A pellet of a cyclic structure-containing polymer (product name “ZEONOR 1430R”, glass transition temperature 138 ° C., manufactured by Nippon Zeon Co., Ltd.) is melted with a short screw extruder at a temperature of 240 ° C. The resin film having a thickness of 100 μm was obtained by melt extrusion. Using this atmospheric pressure plasma surface treatment apparatus (product name “AP-T03-L”, manufactured by Sekisui Chemical Co., Ltd.), this resin film is output 1.5 kW, frequency 25 kHz, nitrogen gas flow rate 50 L / min, irradiation rate 30 cm / min. ) To obtain a pretreated alicyclic structure-containing polymer film.
A small amount of 3-glycidoxypropyltrimethoxysilane (product name “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a sealed container, and the inside of the container was saturated with the vapor of the silane coupling agent. The pre-treated alicyclic structure-containing polymer film obtained above is put here, and kept at 25 ° C. for 15 minutes so that the liquid surface of 3-glycidoxypropyltrimethoxysilane does not touch the film sample. Then, the treatment by the vapor treatment method was performed. This was appropriately cut to obtain a large number of surface-modified resin films having a square of 60 mm square.

(1-4. Evaluation of surface-modified glass substrate)
After matching the treated surface of the surface modified glass substrate obtained in the step (1-2) with the treated surface of the surface modified resin film obtained in the step (1-3), a laminator (manufactured by MCK Co., Ltd.) , ML-300T). The lamination conditions were a pressure of 0.4 MPa and a temperature of 130 ° C.
This was peeled off under the conditions of a temperature of 23 ° C., a peeling speed of 50 mm / min, and a peeling angle of 180 °, and the peel strength (kg / mm ² ) was determined. Table 1 shows the processing time of the one with the shortest processing time among the values obtained with a bonding strength of 0.1 kg / mm ² or more.

<Examples 2-5 and Comparative Examples 1-2>
In step (1-2), the concentration of 3-aminopropyltrimethoxysilane in the processing gas 1 (percentage with a saturation concentration of 100%) or the flow rate of the processing gas 1 in the container 21 is shown in Table 1. A surface-modified glass substrate was prepared and evaluated in the same manner as in Example 1 except that the changes were made as shown. The results are shown in Table 1.

<Example 6>
3-aminopropyltrimethoxysilane (product name “KBM-903”, manufactured by Shin-Etsu Chemical Co., Ltd.) vaporized using a vaporizer (VU-550: manufactured by Lintec Corporation), nitrogen and water vapor were mixed, A processing gas 2 was generated. In this processing gas 2, the concentration of 3-aminopropyltrimethoxysilane was 90% of the saturation concentration, and the water vapor concentration was 80% of the saturation concentration.
In the step (1-2), the processing gas 2 obtained above was used as the processing gas instead of the processing gas 1. Furthermore, the flow rate of the processing gas 1 in the container 21 was set to 100 cm / sec. Except for the above points, a surface-modified glass substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 7>
(7-1. Steam treatment)
The pretreated glass substrate obtained in the step (1-1) of Example 1 is subjected to water vapor treatment by bringing it into contact with water vapor generated by a steam humidifier or the like, and the pretreated and water vapor treated glass substrate is obtained. Got.

(7-2. Production and evaluation of surface modified glass substrate)
Instead of the pretreated glass substrate obtained in the step (1-1), the pretreated and water vapor treated glass substrate obtained in the step (7-1) was used immediately after the water vapor treatment. Furthermore, the flow rate of the processing gas 1 in the container 21 was set to 100 cm / sec. Other than the above points, a surface-modified glass substrate was produced and evaluated in the same manner as in Steps (1-2) to (1-4) of Example 1. The results are shown in Table 1.

<Example 8>
Instead of the glass substrate, a single crystal sapphire substrate (thickness 1.0 mm, manufactured by Kyocera) was used. Furthermore, the flow rate of the processing gas 1 in the container 21 was set to 100 cm / sec. Except for the above points, a surface-modified glass substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 9>
(9-1. Production and pretreatment of resin film)
A pellet of an alicyclic structure-containing polymer (product name “ZEONOR 1430R”, glass transition temperature 138 ° C., manufactured by Nippon Zeon Co., Ltd.) is melted with a short-screw extruder at a temperature of 240 ° C., and a T-die having a temperature of 240 ° C. Was melt extruded to obtain a resin film having a thickness of 100 μm.
After cutting this resin film into a 60 mm square, on one side, using an atmospheric pressure plasma surface treatment device (product name “AP-T03-L”, manufactured by Sekisui Chemical Co., Ltd.), an output of 1.5 kW, a frequency Atmospheric pressure plasma irradiation was performed at 25 kHz, a nitrogen gas flow rate of 50 L / min, and an irradiation speed of 30 cm / min to obtain a pretreated resin film.

(9-2. Treatment of resin film with silane coupling agent)
3-glycidoxypropyltrimethoxysilane (product name “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.) vaporized using a vaporizer (VU-550: manufactured by Lintec Corporation) and nitrogen were mixed, A processing gas 3 was generated in which the concentration of glycidoxypropyltrimethoxysilane was 90% of the saturation concentration.
The processing gas 3 was introduced from the inlet 22 of the container 21 shown in FIG. 2 and discharged from the outlet 23 to circulate the container 21. In this state, the pretreated resin film obtained in the step (9-1) is put in the container 21, and one side of the resin film (in the figure, on the upper surface 11S of the pre-processed molded body 11). Silane coupling agent treatment was performed by bringing the treatment gas 3 into contact for a predetermined time to obtain a surface-modified resin film.
At the time of processing, the flow velocity of the processing gas 3 is an anemometer 24 (manufactured by Tonic Co., Ltd .: pasted wind speed / air temperature probe QB-5, digital 1CH anemometer GeY-10DA) at a height of 5 mm from the surface 11S of the substrate 11. It was used to monitor and adjusted to 100 cm / sec. Moreover, the processing time set different time in each of many resin films. The processing time was appropriately set to 3 seconds, 5 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, and further thereafter increasing at 10-second intervals.

(9-3. Production of surface-modified glass substrate for evaluation)
A glass substrate (thickness 0.7 mm, manufactured by Corning, trade name “Eagle XG”) was cut into a square of 50 mm square, and then an atmospheric pressure plasma surface treatment device (product name “AP-T03-L”, Sekisui Chemical Co., Ltd.) was used to perform atmospheric pressure plasma irradiation at an output of 1.5 kW, a frequency of 25 kHz, a nitrogen gas flow rate of 50 L / min, and an irradiation rate of 30 cm / min, to obtain a pretreated glass substrate.
A small amount of 3-aminopropyltrimethoxysilane (product name “KBM-903”, manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a sealed container, and the inside of the container was saturated with the vapor of the silane coupling agent. The pretreated glass substrate obtained above is put here, and the liquid surface of 3-aminopropyltrimethoxysilane is kept from touching the glass substrate, and kept at 25 ° C. for 15 minutes. A number of surface-modified glass substrates were obtained.

(9-4. Evaluation of surface-modified glass substrate)
After combining the treated surface of the surface modified resin film obtained in the step (9-2) and the treated surface of the surface modified glass substrate obtained in the step (9-3), a laminator (manufactured by MCK Co., Ltd.) , ML-300T). The lamination conditions were a pressure of 0.4 MPa and a temperature of 130 ° C.
This was peeled off under the conditions of a temperature of 23 ° C., a peeling speed of 50 mm / min, and a peeling angle of 180 °, and the peel strength (kg / mm ² ) was determined. Table 1 shows the processing time of the one with the shortest processing time among the values obtained with a bonding strength of 0.1 kg / mm ² or more.

<Comparative Examples 5 and 6>
In step (9-2), the concentration of 3-glycidoxypropyltrimethoxysilane in the processing gas 3 (percentage with a saturation concentration of 100%) or the flow rate of the processing gas 3 in the container 21 is expressed as follows. A surface-modified resin film was prepared and evaluated in the same manner as in Example 9 except that the change was made as shown in 1. The results are shown in Table 1.

<Example 10>
As a resin film, in place of the alicyclic structure-containing polymer film, a polycarbonate film (trade name “Opcon”, manufactured by Keiwa Co., Ltd., thickness 110 μm) was used in the same manner as in Example 9, A surface-modified resin film was prepared and evaluated. The results are shown in Table 1.

<Comparative Examples 7 and 8>
Instead of the alicyclic structure-containing polymer film, a polycarbonate film (manufactured by Keiwa Co., Ltd., trade name “OPCON”, thickness 110 μm) was used as the resin film. Furthermore, in the step (9-2), the concentration of 3-glycidoxypropyltrimethoxysilane in the processing gas 3 (percentage with a saturation concentration of 100%) or the flow rate of the processing gas 3 in the container 21 is set. The changes were made as shown in Table 1. Except for the above points, a surface-modified resin film was prepared and evaluated in the same manner as in Example 9. The results are shown in Table 1.

<Examples 11 to 13>
As a silane coupling agent added to the processing gas 1 in the step (1-2), instead of 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane (Example 11, product name “KBM-803”, Shin-Etsu Chemical Co., Ltd.), 3-isocyanatopropyltriethoxysilane (Example 12, product name “KBE-9007”, manufactured by Shin-Etsu Chemical Co., Ltd.), or vinyltrimethoxysilane (Example 13, product name “KBM-803”), Shin-Etsu Chemical Co., Ltd.) was used. Furthermore, the flow rate of the processing gas 1 in the container 21 was set to 100 cm / sec. Except for the above points, a surface-modified glass substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

The abbreviations in the table indicate the following.
COP: Polymer containing alicyclic structure (product name “Zeonor 1430R”)
PC: Polycarbonate film (trade name “OPCON”)
* 1: The processing gas contains water vapor in addition to the silane coupling agent.
* 2: Steam treatment was performed prior to the silane coupling agent treatment.

  As shown in Table 1, in the examples in which the concentration of the silane coupling agent in the processing gas and the flow rate of the processing gas are within the specified range of the present invention, the adhesion required in a short time compared to the corresponding comparative example. The remarkable effect that power is acquired is acquired. In particular, in Example 6 in which water vapor was added to the processing gas and Example 7 in which water vapor treatment was performed on the glass substrate, the flow rate was not so high, but in a time as short as Example 1 having a higher flow rate. Necessary adhesion was obtained.

11: Molded body 11S: Surface 21: Container 22: Inlet 23: Discharge port 24: Anemometer 31: Container 32: Apparatus for vaporizing silane coupling agent 33: Blower 41: Nozzle 51: Shower head

Claims (5)

A method for producing a surface-modified molded article,
A step of bringing a gas containing a vaporized silane coupling agent into contact with the surface of a pre-processed molded body made of a resin, an inorganic material, or a combination thereof;
The concentration of the silane coupling agent in the gas is 20% or more and 100% or less of the saturation concentration,
The manufacturing method in which the component parallel to the surface of the pre-processed molded body of the gas flow velocity at a height of 5 mm from the surface of the pre-processed molded body is 10 cm / sec or more in the contacting step.   The manufacturing method according to claim 1, wherein in the contacting step, the gas further contains water vapor.   The manufacturing method of Claim 1 or 2 which further includes the process of exposing the said molded object before a process to water vapor | steam prior to the said process to contact.   The manufacturing method of any one of Claims 1-3 whose said molded object before a process contains resin and whose said resin is resin containing an alicyclic structure containing polymer.   The surface treatment method according to any one of claims 1 to 4, wherein the molded body before treatment includes an inorganic material, and the inorganic material is a material including glass.

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