JP6749683B1 - Hydrophilic reinforced molded product made of silicone rubber and hydrophilic reinforced joined product using the same - Google Patents

Abstract

It can be used for microfluidic devices that are difficult to adsorb reagents and easy to send liquid, and cell culture devices that are easy to collect without adhering cultured cells, and the contact angle with water is sufficiently hydrophilic to about 30 ° or less, and it is long. Silicone rubber hydrophilic reinforcement that can be maintained hydrophilic for a period of time, can develop a small contact angle with water in a short time even when in contact with water such as aqueous reaction reagent solution or culture solution, and can be bonded to a support or the like. Provided is a molded body and a hydrophilic reinforced joint using the molded body. In the hydrophilic reinforced molded product made of silicone rubber, the hydrophilic surface due to the addition of the hydrophilic group-containing compound-containing additive to the silicone rubber is a UV irradiation treated surface, an Exima UV irradiation treated surface, a corona discharge treated surface, and a plasma. The surface is hydrophilically strengthened and modified by being a dry-type treated surface selected from a treated surface, an electron beam irradiation-treated surface, and a γ-ray irradiation-treated surface. In the hydrophilic reinforced joint, a hydrophilic reinforced molded product made of silicone rubber and a support are joined.

Description

TECHNICAL FIELD The present invention relates to a hydrophilic-reinforced molded article made of silicone rubber in which the hydrophilicity of the surface of the silicone rubber to which hydrophilicity has been imparted by a hydrophilic group-containing compound-containing additive is enhanced, and a hydrophilic-reinforced joined article.

Using a small amount of a test liquid such as a biological sample such as blood or urine, the specific substrate selectivity of the enzyme is used to develop the amount of enzyme reaction that interacts with the substrate in the sample and its basic mass with the enzyme or the substrate. Analysis by quantifying the degree of coloring by the reagent to be used, or by using the enzyme-containing membrane to convert the enzyme reaction amount into an electric signal at the electrode to quantify the base mass, DNA extraction and PCR amplification (polymerase chain reaction amplification) Microfluidic devices such as microchemical chips have been used to measure ion concentrations and micro-synthesize DNA or proteins or peptides.

Subculture of various cells such as suspension cells and adherent cells, especially subculture of suspension cells, is performed by diluting suspension cells suspended in a medium such as a culture solution and continuing the growth. Cell culture devices such as culture vessels and culture plates are used.

The flow path of such a microfluidic device or the culture solution contact surface of a cell culture device for subculture of floating cells is desirably hydrophilic with a contact angle with water of about 30° or less.

To improve the hydrophilicity of these microfluidic devices and culture vessels, various surface hydrophilization treatments are performed.

When these microfluidic devices and culture vessels are molded silicone products such as silicone rubber and silicone resin, it is known that the surface hydrophilization treatment is performed by surface treatment such as dry treatment or hydrophilic treatment. ing.

As such a surface hydrophilicity-imparting treatment, a dry treatment for modifying the surface of the silicone-made molded product, or a hydrophilic coating agent (for example, a hydrophilic silane coupling agent) is chemically bonded to the surface of the silicone-made molded product and introduced. There is surface modification treatment. With such a surface modification treatment, the hydrophilicity can be maintained for about 3 to 6 months, but the hydrophilicity is not so high that the contact angle with water cannot be reduced to about 30°, or the hydrophilic coating bonded on the surface. The agent molecules gradually sneak from the surface of the silicone molded body to the inside, exposing the silicone molecules and decreasing the hydrophilicity, and there are very few types of hydrophilic coating agents applicable to silicone rubber. It is difficult to develop hydrophilicity. Further, when the support or the like is bonded to the surface-treated surface, surface treatment or chemical modification for bonding must be separately performed, which hinders the hydrophilicity of the corners.

As another surface hydrophilicity imparting treatment, by adding a hydrophilic additive such as a hydrophilic oil to a liquid or millable silicone raw material as a raw material and curing the raw material to form a silicone molded article, the surface is hydrophilically added. There is a material modification treatment that exposes the agent to impart hydrophilicity. As an example of such a material modification treatment, in Patent Document 1, (a) a step of preparing a master having a predetermined fine structure on the upper surface, and (b) PDMS prepolymer on the fine structure formation surface side of the master. A step of injecting a mixture of a curing agent and a polyether-modified surfactant, (c) a step of oxygen plasma-treating the side of the molded PDMS sheet on which the fine structure is formed, (d) the PDMS sheet And a step of applying an organosilane solution to the side of the fine structure forming surface of the PDMS sheet, the method of manufacturing a PDMS sheet having permanent hydrophilicity is disclosed. Generally, in the material modification treatment, the degree of hydrophilicity is not so high that the contact angle with water cannot be reduced to about 30°, and it takes 10 minutes or more to develop hydrophilicity when contacted with water. It is difficult to develop sufficient hydrophilicity, such as

JP, 2006-181407, A

The present invention has been made to solve the above-mentioned problems, and can be used in a microfluidic device that is difficult to adsorb a reagent and is easy to feed, or a cell culture device that is easy to collect without adhering cultured cells, and with water. The contact angle is sufficiently hydrophilized to about 30° or less, and it can be kept hydrophilized for a long period of time. It is an object of the present invention to provide a hydrophilic reinforced molded product made of silicone rubber that can be expressed and can be bonded to a support or the like. Another object of the present invention is to provide a hydrophilic reinforced joined body which can be applied to a microfluidic device by using the silicone rubber hydrophilic reinforced molded body.

In order to achieve the above-mentioned object, the silicone rubber hydrophilic reinforced molded article of the present invention has a hydrophilic surface formed by compounding the silicone rubber with a hydrophilic group-containing compound-containing additive, and is subjected to UV irradiation treatment. By the dry treatment surface selected from the surface, the excimer UV irradiation treatment surface, the corona discharge treatment surface, the plasma treatment surface, the electron beam irradiation treatment surface, and the γ ray irradiation treatment surface, the surface is enhanced in hydrophilicity and modified. According to another aspect of the present invention, there is provided a hydrophilic reinforced molded article made of silicone rubber, wherein the hydrophilic group-containing compound-containing additive is a polyether-modified silicone oil .

In this silicone rubber hydrophilic reinforced molding, the hydrophilic group-containing compound-containing additive is preferably a polyether.

In this silicone rubber hydrophilic reinforced molding, it is more preferable that the hydrophilic group-containing compound-containing additive is a polyether-modified silicone oil as the polyether.

In the hydrophilically strengthened molded product made of silicone rubber, the hydrophilic group-containing compound-containing additive is more preferably the polyether-modified silicone oil composed of a silicone compound having a polyether group in the side chain of the polysiloxane skeleton.

In this silicone rubber hydrophilic reinforced molding, the hydrophilic group-containing compound-containing additive may have an HLB value of 3.5 to 16.9.

This silicone rubber hydrophilic reinforced molded product is blended with 0.1 to 30 parts by mass, preferably 3 to 5 parts by mass of the hydrophilic group-containing compound-containing additive with respect to 100 parts by mass of the silicone rubber. It is that.

In this hydrophilic reinforced molded product made of silicone rubber, the silicone rubber is, for example, an addition-type silicone rubber, a condensation-type silicone rubber, a peroxide-crosslinking-type silicone rubber, an ultraviolet-curing-type silicone rubber, and/or a radiation-crosslinking-type silicone rubber. There is.

This silicone rubber hydrophilic reinforced molded article is a flat sheet, flat plate, or chip; a plate having irregularities on the surface; or a three-dimensional container, a culture plate having wells, a petri dish, having irregularities on the surface. A molded body;

It is more preferable that the silicone rubber-made hydrophilic reinforced molded product is an autoclave sterilized silicone rubber-made hydrophilic reinforced molded product or a heat-treated silicone rubber-made hydrophilic reinforced molded product.

It is even more preferable that the silicone rubber hydrophilic reinforced molded article be transparent or translucent.

The method for producing a hydrophilic reinforced molded product made of silicone rubber of the present invention made to achieve the above-mentioned object is to add a hydrophilic group-containing compound-containing additive which is a polyether-modified silicone oil to a silicone rubber raw material component. The step of curing to form a molded article having a hydrophilic surface, and the surface is selected from UV irradiation treatment, excimer UV irradiation treatment, corona discharge treatment, plasma treatment, electron beam irradiation treatment, and γ-ray irradiation treatment. And a step of performing a dry treatment performed to produce a hydrophilic reinforced molded body made of silicone rubber.

The hydrophilic reinforced conjugate of the present invention made to achieve the above-mentioned object has a hydrophilic surface due to the addition of a hydrophilic group-containing compound-containing additive that is a polyether-modified silicone oil to a silicone rubber. , UV irradiation-treated surface, excimer UV irradiation-treated surface, corona discharge-treated surface, plasma-treated surface, electron beam-treated surface, and γ-ray-treated surface are dry-treated surfaces, thereby enhancing hydrophilicity of the surface. The hydrophilic and reinforced molded body made of silicone rubber that has been modified is bonded to the support.

In this hydrophilic reinforced joined body, it is preferable that the hydrophilic reinforced molded article made of silicone rubber is joined on the surface thereof and on the uneven surface of the support.

It is more preferable that this hydrophilic reinforced joined body is a microfluidic device by having the unevenness serving as a flow path on the uneven surface.

In this hydrophilic reinforced joined body, the surface of the hydrophilic reinforced molded body made of silicone rubber and the support are joined by adhesion by physical adsorption and/or covalent bond by molecular adhesion. And even more preferable.

The silicone rubber hydrophilic reinforced molding of the present invention is one in which the hydrophilicity of the surface of the silicone rubber to which the hydrophilic group-containing compound-containing additive has imparted hydrophilicity is further reinforced by dry treatment. This silicone rubber-reinforced hydrophilic molded article has a sufficiently high hydrophilicity up to a contact angle with water of about 30° or less and can be kept hydrophilic for a long period of time for one year or longer.

This silicone rubber-reinforced hydrophilic molded article can develop a small contact angle with water in a short time even when contacted with water such as an aqueous solution of a reaction reagent or a culture solution.

This silicone rubber-reinforced hydrophilic molded article has high hydrophilicity, but since the silicone rubber is unlikely to interact with the reagent, it is difficult to adsorb the reagent. Therefore, this silicone rubber-made hydrophilic reinforced molded article can be applied to a microfluidic device that easily feeds a liquid without clogging a reagent.

In addition, this silicone rubber hydrophilic reinforced molding has no cytotoxicity and does not adhere to cultured cells such as floating cells and adherent cells. Therefore, the silicone rubber hydrophilic reinforced molding is suitable for cell culture and can be applied to a cell culture device in which cultured cells are easily collected.

The hydrophilic reinforced molded body made of silicone rubber can be bonded to a support or the like such as a hydrophilic reinforced molded body made of silicone rubber, or can be bonded to a support made of various materials by adhesion. Can be used to make

This silicone rubber-reinforced hydrophilic molded article exhibits high hydrophilicity and can exhibit strong bonding strength when bonded. Moreover, when bonded, it exhibits strong peel strength during initial storage, aging, and long-term storage, and also exhibits characteristics that make it difficult to peel when immersed in alcohol, aqueous solution, etc., so it has excellent peel resistance, water resistance, and chemical resistance. And has a high reliability.

In addition, this silicone rubber-reinforced hydrophilic molded article retains the hydrophilicity almost unchanged from the initial state even after a long period of time. Moreover, the hydrophilic surface can maintain its hydrophilicity for a long period of time even when subjected to medical electron beam sterilization or γ-ray sterilization.

Furthermore, since this hydrophilic hydrophilic molded body made of silicone rubber has less than half the adsorption of proteins such as albumin due to being hydrophilic compared to untreated silicone rubber, it can be used for culture plates such as cell culture. It can be used as a culture container.

This hydrophilic-reinforced conjugate can be used in a microfluidic device or a cell culture device, and since it can maintain hydrophilicity, it can stably exhibit its function even after long-term storage.

FIG. 1 is a schematic cross-sectional view showing a silicone rubber hydrophilic reinforced molded body to which the present invention is applied and a hydrophilic reinforced joined body using the same. It is a perspective view which shows another silicone rubber hydrophilic-reinforced molded body to which this invention is applied, and a hydrophilic-reinforced joined body using the same. It is a figure which shows as a side photograph the contact angle with water in the silicone rubber hydrophilic reinforced molded object to which this invention is applied, and the molded object to which this invention is not applied. It is a figure which shows the time-dependent change of the contact angle with water in the silicone rubber hydrophilic reinforced molded object to which this invention is applied, and the molded object to which this invention is not applied. FIG. 3 is a graph showing a contact angle with water before autoclave sterilization treatment and a change with time of the contact angle with water after autoclave sterilization treatment in a graph in a silicone rubber hydrophilic reinforced molding to which the present invention is applied. .. It is a figure which shows the cell adhesiveness in the silicone rubber hydrophilic reinforced molding to which this invention is applied as a micrograph. FIG. 3 is a schematic perspective view showing a laminated hydrophilic reinforced joined body formed using a silicone rubber hydrophilic reinforced molded body to which the present invention is applied.

Hereinafter, modes for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to these modes.

As shown in FIGS. 1 and 2, the silicone rubber hydrophilic reinforced molded product 10 of the present invention is made of silicone rubber containing a hydrophilic group-containing compound-containing additive. The hydrophilic reinforced molded body 10 made of silicone rubber contains the hydrophilic group-containing compound-containing additive, so that the hydrophilic group of the hydrophilic group-containing compound is exposed on the surface 10a, and the surface 10a is It is made hydrophilic and hydrophilic. The surface 10a is a dry-processed surface by being dry-processed, and is hydrophilically strengthened and modified.

Examples of the dry treatment include UV (normal ultraviolet) irradiation treatment, excimer UV irradiation treatment, corona discharge treatment, plasma treatment, electron beam irradiation treatment, and γ-ray irradiation treatment. Among them, excimer UV irradiation treatment and corona discharge treatment are mentioned. Treatment or plasma treatment is preferred. By these treatments, hydrophilicity can be expressed, or bonding can be expressed so as to be compatible with each other. Of these, excimer UV treatment, corona discharge treatment, and plasma treatment are preferable. Preferably an excimer UV treatment can be sustained express hydrophilicity irradiation intensity of 60~600mJ / cm ^2, more preferably by both the bonding property between hydrophilicity irradiation intensity of 400~600mJ / cm ² Can be expressed. In the corona discharge treatment, a combination of treatment speed: 30 to 200 mm/s and treatment number: 3 to 10 times (output voltage: about 15 kV) can exhibit hydrophilicity or hydrophilicity can be sustained. In the plasma treatment, hydrophilicity can be developed and maintained in an irradiation time of 15 to 180 s (output power: about 150 W) under an atmospheric pressure atmosphere, and more preferably, hydrophilicity and bonding can be achieved in an irradiation time of 30 to 180 s. It can be made compatible and expressed.

By these dry processes, the surface 10a of the silicone rubber hydrophilic reinforced molding 10 is UV irradiation treated surface, excimer UV irradiation treated surface, corona discharge treated surface, plasma treated surface, electron beam irradiated treated surface, or γ ray irradiated. The surface is treated.

Silicone rubber is particularly preferable because it becomes possible to express particularly sufficient hydrophilicity by excimer UV irradiation treatment, corona discharge treatment, and/or plasma treatment, and among them, excimer UV irradiation treatment and/or plasma treatment is particularly preferable. This makes it possible to achieve particularly sufficient hydrophilicity and strong bondability at the same time, which is more preferable.

With such a dry-treated surface, the hydrophilicity of the surface 10a is strengthened, and the contact angle with water is 30° or less, preferably 20° or less, and more preferably 10° or less. Such a low contact angle can be stably maintained for a long period of time, for example, several months to about one year or more. Therefore, the surface 10a can be maintained with the hydrophilicity being strengthened. On the other hand, the contact angle with water is 100° or more on the surface of a simple silicone rubber, and the contact angle with water is not applied on the surface of a silicone rubber which is not treated by dry treatment with an additive containing a compound containing a hydrophilic group. Of about 50 to 70° or more, about 90° or more, and on a surface of a silicone rubber that has been dry-processed, for example, excimer UV treatment, the contact angle with water is about 50° or more even immediately after the process. It will be about 100° or more within a day or a month.

で表されるシリコーン化合物（式（１）中、ｘ及びｙはその化合物のシロキシ構造繰り返しユニット数であり、ｘ又はｙが示す繰り返しユニットはブロック共重合体ユニットであってもよくランダム共重合体ユニットであってもよい。ｎはポリエーテル基中のエーテル構造繰り返し数、より具体的には平均で１２程度の数である。Ｒの夫々はメチル基又はフェニル基である）が挙げられる。Examples of the hydrophilic group-containing compound-containing additive include polyether, and specifically, a modified polyoxyethylene compound having a polyoxyethylene group and modified with a functional group, or a polysiloxane in a side chain of a polysiloxane skeleton. Examples thereof include polyether-modified silicone oil containing a hydrophilic group-containing compound such as a silicone compound having an ether group. As such a hydrophilic group-containing compound, the following chemical formula (1)

The silicone compound represented by the formula (in the formula (1), x and y are the number of repeating units of the siloxy structure of the compound, and the repeating unit represented by x or y may be a block copolymer unit or a random copolymer. N may be a unit, and n is the number of repeating ether structures in the polyether group, more specifically an average number of about 12. Each R is a methyl group or a phenyl group.

The hydrophilic group-containing compound-containing additive may be a commercially available product, such as TI-2011 (manufactured by Toray Dow Corning; trade name; see Chemical Formula (1)), TI-6021 (manufactured by Toray Dow Corning). Trade name), TSF-4445 (manufactured by Momentive Performance Materials Japan; trade name), TSF-4446 (manufactured by Momentive Performance Materials Japan, trade name), KF-6011 (Shin-Etsu Chemical Co., Ltd.) Company name; KF-6011P (Shin-Etsu Chemical Co., Ltd. product name), KF-6012 (Shin-Etsu Chemical Co., Ltd. product name), KF-6015 (Shin-Etsu Chemical Co., Ltd. product name), KF -6004 (manufactured by Shin-Etsu Chemical Co., Ltd.; trade name), KF-6043 (manufactured by Shin-Etsu Chemical Co., Ltd.; trade name), Tween 20 (manufactured by Sigma-Aldrich Co., trade name) which is polyethylene glycol sorbitan monolaurate. ..

It is sufficient that such a hydrophilic group-containing compound-containing additive has an HLB value (Hydrophilic-Lipophilic Balance; hydrophilic oil balance) of 3.5 to 16.9, for example, 4.5 to 16.9. It can exhibit hydrophilicity. If the HLB value is smaller than this range, the hydrophilicity on the surface of the silicone rubber hydrophilic reinforced molding 10 will be insufficient, and if it is larger than this range, the dispersibility in a hydrophobic material will be significantly reduced. .. Regarding the HLB value, for ester-based surfactants, the saponification value is S, the acid value of the fatty acid that constitutes the surfactant is A, and the HLB value is defined as 20 (1-S/A), and the HLB value is Is defined as the sum of the formula weights of 20×hydrophilic part/molecular weight and the number of groups determined by the functional group (for example, a methyl group or a methylene chain is 0.475 as a lipophilic group, and a hydroxyl group is 1.9 as a hydrophilic group). Etc.), the HLB value is defined by 7 + the sum of the number of bases of the hydrophilic group-the sum of the number of bases of the lipophilic group, and the HLB value is 7+11.7 x log (the sum of the formula weights of the hydrophilic part/the formula weight of the lipophilic part). What is defined by the sum of) is known.

In the silicone rubber-made hydrophilic reinforcing molding 10, such a hydrophilic group-containing compound-containing additive is 0.1 to 30 parts by mass, preferably 1 to 10 parts by mass, and more preferably 100 parts by mass of the silicone rubber. It is preferable that 3 to 10 parts by mass, specifically 3 to 5 parts by mass, be blended. Below this range, the hydrophilicity will be insufficient, and above this range, bleed-out will occur.

Examples of the raw material of the silicone rubber in the silicone rubber hydrophilic reinforced molding 10 include liquid or millable silicone raw materials. The silicone rubber of the hydrophilic reinforced molded body 10 made of silicone rubber is an addition-type silicone rubber, a condensation-type silicone rubber, a peroxide-crosslinking-type silicone rubber, an ultraviolet-curing-type silicone rubber, and/or a radiation-crosslinking-type silicone rubber, among them. Examples thereof include thermosetting liquid silicone rubber which is an addition type silicone rubber, and millable silicone rubber which is a peroxide crosslinking type or an addition crosslinking type.

The shape of the silicone rubber hydrophilic reinforced molded body 10 is not particularly limited, but it is a flat surface having no irregularities, a film having a thickness of 1 to 15 μm coated on any film, a sheet having a thickness of 15 μm to 1000 μm, and a thickness of 1 mm to 10 mm. Plate, a chip having a side length of 1 mm to 300 mm cut from them, or a flat sheet, a flat plate, or a chip may be used, and the surface 10a is subjected to fine processing on the order of nanometers (1-1000 nm). The plate may be a plate having finely processed irregularities, a container such as a three-dimensional petri dish or a flask, a culture plate having wells, or a molded article having finely processed surface irregularities.

The silicone rubber hydrophilic reinforced molded body 10 does not have a decreased contact angle with water even when subjected to autoclave sterilization treatment or heat treatment. Specifically, when subjected to autoclave sterilization treatment by exposing to steam under autoclave sterilization conditions such as 121° C. and 2 atm under high temperature and high pressure, the contact angle with water is 20° or less, preferably 10° Keep reduced to below °. The mechanism is not necessarily clear, but the molecular movement of the hydrophilic group-containing compound-containing additive is activated by steam, and the hydrophilic group is exposed on the surface 10a and is stabilized while being exposed. It is presumed that.

The transparency of the hydrophilic reinforced molded product 10 made of silicone rubber can be adjusted by the thickness and the compounding amount of the hydrophilic group-containing compound-containing additive, but by adjusting the thickness to 15 μm to 2 mm, and/or the silicone rubber. It is preferable that the hydrophilic group-containing compound-containing additive is blended in an amount of 0.1 to 30 parts by weight, preferably 3 to 5 parts by weight, based on 100 parts by weight, so as to be transparent or translucent. Among them, when the thickness is 15 μm to 500 μm, more preferably 100 μm, and the amount of the hydrophilic group-containing compound-containing additive is 3 to 5 parts by mass, it is sufficiently transparent for optical analysis by ultraviolet rays or infrared rays, magnifying observation with a microscope, and the like. Develop sex.

The silicone rubber hydrophilic reinforcing molding 10 can be manufactured, for example, as follows.

First, a silicone rubber raw material component containing a cross-linking agent and a curing agent as necessary is blended with the predetermined amount of the hydrophilic group-containing compound-containing additive, kneaded and stirred, and defoamed if necessary. .. This kneaded product is molded into the desired shape, for example, a sheet, and is crosslinked by heating to be cured into silicone rubber to form a molded body 10 having the desired shape. By exposing the hydrophilic group-containing compound to the surface 10a of the molded body 10 thus obtained, the surface 10a becomes hydrophilic.

Then, the surface 10a of the obtained molded body 10 is subjected to a dry treatment, for example, a UV irradiation treatment, an excimer UV irradiation treatment, a corona discharge treatment, a plasma treatment, an electron beam irradiation treatment, and/or a γ-ray irradiation treatment. The hydrophilicity of 10a is strengthened, the contact angle with water becomes small, the hydrophilicity becomes high, and the high hydrophilicity can be maintained for a long time. After this dry treatment, it can be kept highly hydrophilic in a clean room environment or at room temperature, atmospheric pressure and atmospheric humidity for a long period of time, for example, for a year or more, and its contact angle with water can be kept low. It can be confirmed that contact angle measurement conditions, for example, 30° or less, preferably 10° or less, can be maintained even when measured 10 seconds to 4 minutes after dropping the water droplets.

As shown in FIGS. 1 and 2, in the hydrophilic reinforced joined body 1 of the present invention, a hydrophilic reinforced molded body 10 made of silicone rubber having a thickness of 15 to 500 μm and a support body 20 having a thickness of 15 to 500 μm are joined. Is what The hydrophilic reinforced conjugate 1 serves as a microfluidic device such as a microchemical chip. The hydrophilic-reinforced joint body 1 is arranged so that the surface 10a of the lower surface, which is the joint surface side with the support body 20, is a surface that has been hydrophilically strengthened and modified. The support 20 is, for example, silicone rubber, a silicone rubber hydrophilic reinforced molding, ethylene propylene diene rubber (EPDM), vinylidene fluoride rubber (FKM), tetrafluoroethylene-propylene rubber (FEPM), tetrafluoroethylene-. It is formed of any support selected from purple oro vinyl ether (FFKM), polycarbonate, cycloolefin polymer, acrylic resin, polystyrene, polyethylene, polyethylene terephthalate, various glasses, and various metals.

As an example of the hydrophilic reinforced joined body 1, a case of a microchemical chip will be specifically described.

The support 20 is a single surface having a depth of 5 to 1000 μm and a width of 10 μm or more to be the channels 22 and 23 of the microchemical chip on the surface 20a of the upper surface which is the joint surface side with the hydrophilic strengthening molded body 10 made of silicone rubber, or Concavities and convexities having a plurality of grooves are provided.

In this hydrophilic reinforced joined body 1, a lower surface 10a which is the joining surface side of the silicone rubber hydrophilic reinforced molded body 10 and a non-grooved surface 20a of the upper surface which is the joining surface side of the support 20 are Adhesion by physical adsorption and/or covalent bond by molecular adhesion is possible, preferably by covalent bond by molecular adhesion, so that even if peeled off, it cannot be interfacially peeled and strongly bonded so as to be broken and peeled. ing.

In order to improve the dispersibility of the polyether-modified silicone oil in the silicone rubber, a compound having a hydrophobic main chain and a hydrophilic end, such as a silicone compound having a hydroxy group at the end of the polysiloxane skeleton, is used. Good.

The silicone rubber hydrophilic reinforced molding 10 can be coated on any base material, and may have a two-layer structure in which the silicone rubber hydrophilic reinforced molding is attached to the base material. The hydrophilicity-reinforced molded body made of silicone rubber can be thinned and attached to a highly transparent base material to ensure transparency.

If necessary, the hydrophilic reinforced joined body 1 is bonded to the reinforcing body 30 of the same shape with an adhesive on the lower surface of the support 20, that is, on the non-bonding surface side with the hydrophilic reinforced molded body 10 made of silicone rubber. Good. In particular, when the support body 20 or the reinforcement body 30 is made of rubber, it is possible to perform bonding by molecular adhesion.

In this hydrophilic reinforced joined body 1, since the groove of the support body 20 is not joined to the lower surface 10a which is the joining surface side of the silicone rubber hydrophilic reinforced molded body 10, sufficient hydrophilicity is exhibited. Therefore, the contact angle with water is at most 30°, preferably 20° or less, more preferably 10° or less. As a result, the liquid feeding performance in the flow path as the microfluidic device is enhanced, and clogging can be avoided without involving residual air, dissolved air, or volatile vapor during liquid feeding.

In this hydrophilic reinforced joined body 1, the groove of the support body 20 includes a test liquid injection groove 21a, a chemical liquid injection groove 21b, a flow path 22 extending from them, branch flow paths 23a and 23b branched in the middle, The discharge grooves 24a and 24b. In the hydrophilic reinforced molded body 10 of the hydrophilic reinforced joined body 1, the test liquid injection port 11a and the chemical liquid injection port 11b are opened at positions corresponding to the test liquid injection groove 21a and the chemical liquid injection groove 21b, and discharged. The discharge ports 14a and 14b are opened at positions corresponding to the grooves 24a and 24b.

As shown in FIG. 7, this hydrophilic reinforced joined body 1 is made of various resins or various rubbers, for example, silicone rubber, and is provided with a channel 42 on the lower side surface of the microchannel molded body 40 which can also serve as a support. The hydrophilic injection molding 10 made of silicone rubber of the same shape is bonded to the lower surface of the micro-flow molding 40 through the flow passage 42 and the liquid injection port 44 by, for example, molecular adhesion or an adhesive, and silicone rubber is further added if necessary. A support 20 made of a hard resin such as polycarbonate may be provided on the lower surface of the hydrophilic reinforced molded body 10.

Examples of a silicone rubber hydrophilic reinforced molded body 10 to which the present invention is applied and a hydrophilic reinforced joined body 1 using the same, and a molded body 10 to which the present invention is not applied and a joined body using the same. The comparative example will be described in comparison.

(Example 1)
To 100 parts by mass of the thermosetting liquid silicone rubber raw material, 5 parts by mass of a polyether-modified silicone oil as a hydrophilic group-containing compound-containing additive is blended, and the mixture is kneaded by stirring with a defoaming machine to stir the hydrophilic property. A silicone rubber raw material component composition for forming a reinforced molded body was prepared. This was filled in a resin mold and heat-treated at 120° C. to be heat-cured to obtain a 0.5 mm thick white translucent silicone rubber hydrophilic molded body sheet. This was cut into a length of 3 cm and a width of 1 cm to obtain a silicone rubber hydrophilic molded product chip. By subjecting this chip to excimer UV treatment, a silicone rubber-made hydrophilic reinforced molded article test piece 1 (also referred to as hydrophilic reinforced body 1) having a hydrophilic surface was obtained.

(Comparative Example 1-1)
A resin mold was filled with a composition consisting of only a thermosetting liquid silicone rubber, and heat-treated at 120° C. for thermosetting to obtain a transparent molded sheet having a thickness of 0.5 mm. This was cut into a length of 3 cm and a width of 1 cm to obtain a comparative example molded body test piece 1-1 (also referred to as a liquid material simple substance 1-1).

(Comparative Example 1-2)
The comparative example molded body test piece 1-2 (also referred to as the liquid material simplex excimer treated body 1-2) in which the surface of the molded body comparative test piece 1 manufactured in Comparative Example 1 was subjected to excimer UV treatment Got

(Comparative Example 1-3)
The same silicone rubber-made hydrophilic molded body chip as that manufactured in Example 1 was not subjected to the excimer UV treatment, and a comparative molded body test piece 1-3 (also referred to as a hydrophilic additive-containing non-excimer-treated body 1-3). ) Obtained as.

(Observation of contact angle with water before aging)
One drop of water was dropped on the silicone rubber hydrophilic reinforced molded product example test piece 1 of Example 1 and the comparative example molded product test pieces 1-1 and 1-3 of Comparative Examples 1-1 and 1-3. 3 shows a photograph of water droplets taken from the side after 10 seconds (note that Comparative Example molded body test piece 1-3 of Comparative Example 1-3 is a photograph taken 5 minutes after the dropping of water droplets). is there). The results obtained by measuring the contact angle with water using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science Co., Ltd.) are also shown.

As is apparent from FIG. 3, in the comparative molded body test piece 1-3 (hydrophilic additive-blended non-excimer treated body 1-3), the contact angle is as large as about 50 to 70° even after contact with water droplets for 5 minutes. On the other hand, the contact angle of the silicone rubber hydrophilic reinforced molded product test piece 1 (hydrophilic reinforced product 1) of Example 1 was 10° or less.

(Test 1 for measuring contact angle with water after aging)
The silicone rubber hydrophilic reinforced molded body example test piece 1 of Example 1 and the comparative example molded body test pieces 1-1 to 1-3 of Comparative Examples 1-1 to 1-3 were prepared at a temperature of about 21°C. It was stored for a predetermined number of days in a clean room environment with a relative humidity of about 60 RH%. After a lapse of a predetermined number of days, one drop of water was dropped and 10 seconds later, the contact angle with water was measured with a contact angle measuring instrument automatic contact angle meter DM-501 (Kyowa Interface Science Co., Ltd.; trade name) to be 5 per test piece. Up to 7 points were measured and the average value was calculated. The results are shown together in FIG.

As is apparent from FIG. 4(a), the comparative example molded body test piece 1-1 (liquid material simple substance 1-1), the comparative example molded body test piece 1-3 (hydrophilic additive-blended non-excimer treated body 1-3). Then, the contact angles were about 108° and about 90°, which were very high immediately after the production, and the comparative example molded body test piece 1-2 (liquid material single excimer treated body 1-2) had a considerably high contact angle of about 46°. After about 30 days, it increased to about 100°. On the other hand, in the case of the silicone rubber hydrophilic reinforced molded article test piece 1 (hydrophilic reinforced body 1) of Example 1, the contact angle was as low as about 5° immediately after production, and was about 10° even after 300 days had passed. It is only slightly larger than the error range, and has not changed substantially.

(Example 2)
To 100 parts by mass of the thermosetting liquid silicone rubber, 3 parts by mass of the polyether-modified silicone oil as an additive containing a hydrophilic group-containing compound is blended, kneaded with a stirring/defoaming machine and stirred to enhance hydrophilicity. A silicone rubber raw material component composition for forming a molded body was prepared. This was molded on a resin film and heat-cured to obtain a 0.1 mm thick white translucent silicone rubber hydrophilic molded body sheet. This was cut into a length of 3 cm and a width of 1 cm to obtain a silicone rubber hydrophilic molded product chip. This chip was subjected to excimer UV treatment to obtain a silicone rubber hydrophilic reinforced molded body example test piece 2 (also referred to as hydrophilic reinforced body 2) whose surface was hydrophilically reinforced.

(Comparative Example 2-1)
A composition composed of only thermosetting liquid silicone rubber was molded on a resin film and heat-cured to obtain a transparent silicone rubber hydrophilic molded sheet having a thickness of 0.1 mm. This was cut into a length of 3 cm and a width of 1 cm to obtain a comparative molded article test piece 2-1 (also referred to as a liquid material simple substance 2-1).

(Comparative Example 2-2)
The molded article comparative test piece 2-1 produced in Comparative Example 2-1 was subjected to excimer UV treatment on the surface thereof to perform excimer UV treatment. Comparative example molded article test piece 2-2 (liquid material alone excimer treated article 2- (Also called 2).

(Comparative Example 2-3)
The same silicone rubber-made hydrophilic molded body chip as that manufactured in Example 2 was not subjected to the excimer UV treatment, and the comparative molded body test piece 2-3 (also referred to as a hydrophilic additive-containing non-excimer treated body 2-3). ) Obtained as.

(Contact angle measurement test 2 with water after aging)
The silicone rubber hydrophilic reinforced molded article test piece 2 of Example 2 and the comparative molded article test pieces 2-1 to 2-3 of Comparative Examples 2-1 to 2-3 were heated at a temperature of about 21°C. It was stored for a predetermined number of days in a clean room environment with a relative humidity of about 60 RH%. After a lapse of a predetermined number of days, one drop of water was dropped and 10 seconds later, the contact angle with water was measured with a contact angle measuring instrument automatic contact angle meter DM-501 (Kyowa Interface Science Co., Ltd.; trade name) to be 5 per test piece. Up to 7 points were measured and the average value was calculated. The results are shown together in FIG.

As is clear from FIG. 4B, the comparative example molded body test piece 2-1 (liquid material simple substance 2-1), the comparative example molded body test piece 2-3 (hydrophilic additive-blended non-excimer treated body 2-3). Then, the contact angles immediately after the production were very high at about 97° and about 103°, respectively, and were considerably high at about 78° for the comparative molded article test piece 2-2 (liquid material single excimer treated body 2-2). After about a few days, it increased to about 90°. On the other hand, the silicone rubber hydrophilic reinforced molded product test piece 2 (hydrophilic reinforced product 2) of Example 2 had a low contact angle of about 5° immediately after production, and was about 14° even after 120 days. It is only slightly larger than the error range, and has not changed substantially.

(Reliability test of hydrophilic surface)
The silicone rubber hydrophilic reinforced molded article of Example 2 obtained by the excimer UV treatment Example Test piece 1 is used as a medical rubber product, and the usual irradiation amount for medical electron beam sterilization or γ-ray sterilization is used. When irradiation sterilization was performed at 20 to 50 kGy, which is stronger than 20 to 25 kGy, the hydrophilicity was maintained for 6 months or longer, and the contact angle could be maintained at 20° or less.

(Example 3)
Even when the silicone rubber hydrophilic reinforced molded product example test piece 2 obtained in Example 2 was heat-treated at 120° C. for 20 minutes, it showed high hydrophilicity. Among them, 80° C. showed the same contact angle as in Example 2.

(Example 4)
Example 1 except that 100 parts by mass of the thermosetting liquid silicone rubber was mixed with 3 parts by mass of a polyether-modified silicone oil as a hydrophilic group-containing compound-containing additive and 10 parts by mass of a silanol group-containing polymer at both ends. Even if the excimer UV treatment was performed on the molded body test piece obtained in the same manner as described above, the hydrophilicity developing ability was not inhibited. Further, when visually confirmed, the degree of white translucency of the molded product could be reduced. Furthermore, the contact angle of water was 10° or less even after about 8 months had passed after the excimer UV treatment. From this, it was found that the silanol group-containing polymer at both ends does not inhibit the hydrophilicity expression and improves the hydrophilic effect.
(Comparative example 3)
On the other hand, the molded body obtained in the same manner as in Example 4 except that it was composed only of the polymer containing silanol groups at both ends did not exhibit hydrophilicity even when subjected to dry treatment. Only 10 parts by mass of a compound containing silanol groups at both ends was bleeding out.

(Example 5)
To 100 parts by mass of thermosetting liquid silicone rubber, 5 parts by mass of polyether-modified silicone oil as an additive containing a hydrophilic group-containing compound is blended, kneaded by stirring with a defoaming machine and stirred to enhance hydrophilicity. A silicone rubber raw material component composition for forming a molded body was prepared. This was filled in a resin mold, and heat-treated at 120° C. for thermosetting to obtain a white translucent silicone rubber hydrophilic molded body sheet having a thickness of 2 mm. This was cut into a length of 3 cm and a width of 1 cm to obtain a silicone rubber hydrophilic molded product chip. By subjecting this chip to excimer UV treatment, a hydrophilic rubber-reinforced molded body test piece 5 of a silicone rubber whose surface was hydrophilically strengthened was obtained. Silicone rubber hydrophilic reinforced molded product Example Test piece 5 was obtained by subjecting it to autoclave sterilization conditions of 121° C. and 2 atm for 20 minutes and those not exposed.

(Contact angle measurement test with water after autoclave sterilization and aging)
Silicone rubber hydrophilic reinforced molded article of Example 5 Example Specimen 5 after autoclave sterilization was stored for a predetermined number of days in a clean room environment at a temperature of about 21° C. and a relative humidity of about 60 RH%. Before autoclave sterilization, and after a certain number of days after autoclave sterilization, drop 1 drop of water and 10 seconds later, water with contact angle measuring instrument automatic contact angle meter DM-501 (Kyowa Interface Science Co. Ltd.; trade name) The contact angle with each test piece was measured at 5 to 7 points, and the average value was calculated. The results are summarized in FIG.

As is clear from FIG. 5, the contact angle with water, which was about 20° before the autoclave sterilization treatment, became 10° or less after at least 5 days, which can be maintained until after about 120 days, and after about 180 days. After that, it increased to about 16°, which was only slightly larger than the error range, and did not substantially change.

(Example 6)
Silicone Rubber Hydrophilic Reinforced Moldings Obtained in Examples 1 and 2 Example Excimer UV-irradiated surfaces of test pieces (hydrophilic reinforcers 1 and 2) having the same shape and a silicone rubber thickness of 0.015 to 2 mm , A hydrophilic reinforced molded body or a polycarbonate film support is bonded by molecular adhesion to obtain a hydrophilic reinforced bonded body test piece 6-1 (bonded body with silicone rubber), 6-2 (hydrophilic reinforced molded body). And a 6-3 (a joined body with a polycarbonate film). Regarding the bonded body example test pieces 6-1, 6-2, and 6-3, JIS K 6854-2:1999 Adhesive-Peeling adhesive strength test method-Part 2: Comply with 180 degree peeling at normal temperature and normal pressure A peel test was conducted. Further, the joint body example test piece 6-1 was immersed in water and boiled for 1 hour, or immersed in alcohol for 1 hour, and the peeling test was similarly performed. The results are summarized in Table 1 below.

As is clear from Table 1, when a peeling test was performed on all of the bonded body test pieces 6-1, 6-2, and 6-3 at room temperature and normal pressure, it was confirmed that the rubber fractured and the entire surface was bonded. The joint body example test piece 6-1 was immersed in water, boiled, or immersed in alcohol, and then subjected to a peeling test. As a result, it was confirmed that the rubber broke and the entire surface was adhered. From this, the joined body example test piece of the example to which the present invention is applied has a high initial joining strength, and also has water resistance and chemical resistance even when exposed to the harsh conditions of immersion in boiling water or alcohol. It was revealed that (alcohol resistance) was excellent and the bonding strength remained high.

(Cytotoxicity test 1: Eluent toxicity evaluation test)
The silicone rubber hydrophilic reinforced molded article test pieces obtained in Example 1 were subjected to an eluate toxicity evaluation test as follows. Autoclave sterilization was performed at 121° C. and 2 atm for 20 minutes, or 15 kGy was subjected to electron beam sterilization once at 10 MeV. The eluate from this test piece was suspended in a cell suspension to prepare a culture solution, and HeLa-S3 cells (human cervical cancer cells) were cultured in a polystyrene (PSt) dish. 100% confluence (complete culture of the surface of the culture vessel was confirmed by phase contrast microscope observation). From this, it was confirmed that the eluate had no cytotoxicity.

(Cytotoxicity test 2: Cell adhesion evaluation test)
A cell adhesion evaluation test was carried out on the silicone rubber hydrophilic reinforced molded product example test piece obtained in Example 1. FIG. 6 is a photograph of a phase-contrast microscope observation result of the PSt dish culture vessel, the culture vessel and the liquid material simple substance molded body 1-1, the culture vessel and the sheet of the test piece to which the present invention is applied. Show.

As is clear from FIG. 6, cells on the rubber surface could be observed by a phase-contrast microscope by using a white translucent silicone rubber hydrophilic reinforced molded product as a sheet having a thickness of 0.1 mm. Specifically, while cells were adhered to the PSt dish culture vessel, a smaller number of cell adhesions were observed in the liquid material simple substance molded body than in the PSt dish, but a test to which the present invention is applied One sheet had no cells attached. From this, it was shown that it can be used in unfixed culture applications such as floating cells (for example, a bag for cell culture (recovery of cultured cells is easy)).

(Example 7 and Comparative Example 7)
To 100 parts by mass of the thermosetting liquid silicone rubber, the following hydrophilic oils (8 kinds) as a hydrophilic group-containing compound-containing additive were added in predetermined parts (1 to 5 parts by mass), respectively, and crosslinked at 120°C. A silicone rubber hydrophilic molded rubber test piece (thickness 1 mm) was prepared. Finally, an excimer UV treatment was performed to obtain a silicone rubber hydrophilic reinforced molded product example test piece whose surface was hydrophilically reinforced. In addition, a silicone rubber molded article control example test piece made of silicone rubber was obtained in the same manner except that the hydrophilic oil was not added.
As the hydrophilic oil, TI-2011 which is a polyether modified silicone oil manufactured by Toray Dow Corning; TI-6021 which is a silicone emulsifier (W/O type) manufactured by Toray Dow Corning; Shin-Etsu Chemical Co., Ltd. KF-6004, KF-6011, KF-6012, and KF-6015 (W/Si emulsifier), which are polyether-modified silicone oils manufactured by Momentive; TSF4445 and TSF4446, which are polyether-modified silicone oils manufactured by Momentive Co.; Tween 20, a non-ionic surfactant from Sigma-Aldrich, was used, respectively.

(Contact angle measurement test 3 with water after aging)
The silicone rubber hydrophilic reinforced molded product example test piece of Example 7 and the silicone rubber molded product control example test piece of Control Example 7 were stored in a petri dish under a clean room environment (temperature 21° C., relative humidity 60 RH%). Then, the change with time was examined. As the hydrophilicity evaluation, the contact angle of water after a predetermined time (average value of 5 to 7 points) was measured in the same manner as in Example 1.

(Joint reliability test)
A joint with a radiation-crosslinking type silicone rubber (corona discharge treatment speed: 100 mm/s, number of times: 3 times, gap length: 1 mm) was prepared (thermocompression bonding condition: 12.8 kgf/cm ² , 80° C., 10 minutes). .. In the bonding reliability test, an initial bonding test, an alcohol immersion test, a water boiling test (each n=3), and a 180 degree peeling test were performed in the same manner as described above to evaluate initial resistance, alcohol resistance and water resistance.

As a result of the evaluation, 3 to 5 parts by mass of the hydrophilic oil (KF-6015, TSF4445, TSF4446, TI-2011, KF-6011) hydrophilic oil having an HLB value of 4.5 to 14.5 was added to the silicone rubber hydrophilic molded article. It was confirmed that the silicone rubber hydrophilic reinforced molded product subjected to the excimer UV treatment maintained the hydrophilic property for 3 months. In addition, when 3 parts by mass of compound (KF-6015, TSF4445, TSF4446, TI-2011), the initial, alcohol resistance and water resistance were confirmed by examination of bonding with a radiation crosslinkable silicone rubber. When 1 part by mass of the hydrophilic oil (KF-6011) having an HLB value of 14.5 was blended, it was confirmed that the hydrophilicity was maintained for 3 months. In addition, initial, alcohol resistance, and water resistance were confirmed by examination of bonding with radiation-crosslinking silicone rubber. In the case of blending 5 parts by mass of a hydrophilic oil (Tween 20) having an HLB value of 16.9, it was confirmed that the hydrophilicity was retained for one month and the bonding with the polycarbonate film was performed. From the above results, it was confirmed that, in the HLB value range of 4.5 to 16.9, the silicone rubber hydrophilic reinforced molded article exhibited hydrophilicity and sustained hydrophilic effect. We also confirmed highly reliable bonding with dissimilar materials.

(Example 8 and Comparative Example 8)
In the same manner as in Example 7, except that TI-2011 was used as the hydrophilic group-containing compound-containing additive in a predetermined number (1, 3, 5, 10 parts by mass), respectively, the surface was Hydrophilically reinforced silicone rubber hydrophilic reinforced molded product Example A test piece was obtained. The control example 8 is the same as the silicone rubber molded product control example test piece 8 of the control example 7. Evaluation was carried out in the same manner as in Example 7 and Comparative Example 7.

It was confirmed that the silicone rubber hydrophilic molded body containing 3 to 10 parts by mass of TI-2011 was subjected to excimer UV treatment and the silicone rubber hydrophilic reinforced molded body kept hydrophilic for 3 months. When 1 to 3 parts by mass was compounded, initial, alcohol resistance and water resistance were confirmed by examination of bonding with a radiation crosslinkable silicone rubber. From the above results, it was confirmed that 3 parts by mass of TI-2011 blended silicone rubber hydrophilic reinforced molded article exhibited hydrophilicity, sustained hydrophilic effect, and highly reliable bonding with different materials.

(Example 9 and Comparative Example 9)
In the same manner as in Example 7 except that 3 parts by mass of TI-2011 was used as the hydrophilic group-containing compound-containing additive and the excimer UV treatment conditions were changed, the surface was hydrophilically strengthened. A silicone rubber hydrophilic reinforced molded product Example A test piece was obtained. The control example 9 is a test piece of a control example of a silicone rubber molded article which was not subjected to the excimer UV treatment. Evaluation was carried out in the same manner as in Example 7 and Comparative Example 7. The initial peelability was evaluated by conducting a peel test by hand.

Excimer UV treatment conditions of a hydrophilic molded body made of 3 parts by mass of TI-2011 and made of silicone rubber were examined. For the condition examination, an excimer lamp light source L11751-01 (manufactured by Hamamatsu Photonics KK, trade name) was used, and the distance between the sample and the light source was fixed at 1 mm. When the irradiation intensity was 60 to 600 mJ/cm ² , hydrophilicity development and hydrophilic effect for 3 months were confirmed. At 400 to 1800 mJ/cm ² , initial joining with the radiation crosslinkable silicone rubber was confirmed. From the above results, it was found that when 400 to 600 mJ/cm ² , it is possible to achieve both hydrophilicity development and bonding.

(Example 10 and Comparative Example 10)
In Example 7, 3 parts by mass of TI-2011 was used as the hydrophilic group-containing compound-containing additive, and plasma processing (output power: about 150 W, under atmospheric pressure atmosphere) conditions were changed in place of the excimer UV processing. Except for the above, in the same manner as in Example 7, a silicone rubber hydrophilic reinforced molded article test piece having a hydrophilic surface was obtained. The control example 10 is a test piece of a control example of a silicone rubber molded body which was not subjected to the plasma treatment. Evaluation was carried out in the same manner as in Example 7 and Comparative Example 7. The initial peelability was evaluated by conducting a peel test by hand.

Examination of plasma treatment conditions for hydrophilic molded article made of 3 parts by mass of TI-2011 made of silicone rubber was carried out. For the examination of conditions, a vacuum plasma device YHS-G250 (manufactured by Kaiki Semiconductor Co., Ltd.) was used, and the introduced gas was fixed to air and the output power was fixed to about 150 W. When the irradiation time was 15 to 180 s, the hydrophilicity development and the hydrophilic effect for 3 months were confirmed. At 30 to 180 s, initial joining with the radiation-crosslinking type silicone rubber was confirmed. From the above results, it was found that both hydrophilic expression and bonding can be achieved at 30 to 180 s.

(Example 11 and Comparative Example 11)
Same as Example 7, except that 3 parts by mass of TI-2011 was used as the hydrophilic group-containing compound-containing additive in Example 7 and the conditions were changed to corona discharge treatment instead of excimer UV treatment. Then, a hydrophilic rubber-reinforced molded body test piece of a silicone rubber whose surface was hydrophilically strengthened was obtained. Control Example 11 is a control sample of a silicone rubber molded article that was not subjected to corona discharge treatment. Evaluation was carried out in the same manner as in Example 7 and Comparative Example 7. The initial peelability was evaluated by conducting a peel test by hand.

Examination of corona discharge treatment conditions for a hydrophilic molded body made of 3 parts by mass of TI-2011 and made of silicone rubber was conducted. For the condition examination, a corona scanner ASA-4 (manufactured by Shinko Electric Instrumentation Co., Ltd.) was used, and the output voltage was fixed at about 15 kV and the distance between the sample and the electrode was fixed at 1 mm. When the number of treatments was 3 and the treatment speed was 30 to 100 mm/s, the hydrophilicity development and the hydrophilic effect for 3 months were confirmed. When the processing speed was 200 mm/s, hydrophilicity development and hydrophilic effect for 2 months were confirmed. When the number of treatments was 10 and the treatment speed was 30 mm/s, the hydrophilicity development and the hydrophilic effect for 2 months were confirmed. From the above results, it was found that there is a condition that the hydrophilicity can be exhibited and the hydrophilic effect can be sustained by the combination of the treatment speed: 30 to 200 mm/s and the treatment number: 3 to 10 times.

(Example 12 and Comparative Example 12)
To 100 parts by mass of the thermosetting millable silicone rubber raw material, 3 parts by mass of a polyether-modified silicone oil which is a hydrophilic oil as a hydrophilic group-containing compound-containing additive is added, and crosslinked at 170°C or addition-crosslinked at 120°C. A silicone rubber hydrophilic molded rubber test piece (thickness 1 mm) was prepared. Finally, an excimer UV treatment was performed to obtain a silicone rubber hydrophilic reinforced molded product example test piece whose surface was hydrophilically reinforced. In addition, a silicone rubber molded article control example test piece made of silicone rubber was obtained in the same manner except that the hydrophilic oil was not added. Evaluation was carried out in the same manner as in Example 7 and Comparative Example 7. The initial peelability was evaluated by conducting a peel test by hand.

The peroxide-crosslinkable or addition-crosslinkable millable silicone rubber hydrophilic moldings are treated with excimer UV-treated peroxide-crosslinkable or addition-crosslinkable millable silicone rubber hydrophilic moldings, both of which are hydrophilic for one month. The retention of sex was confirmed. From this, it was confirmed that, in addition to the liquid silicone rubber, the millable silicone rubber also exhibited hydrophilicity and sustained hydrophilic effect. In addition, initial bonding with the radiation-crosslinking type silicone rubber was confirmed regardless of the crosslinking form.

(Example 13 and Comparative Example 13)
The silicone rubber hydrophilic reinforced molded product example test piece and the silicone rubber molded product control example test piece produced in Example 7 and Comparative Example 7 were each immersed in an albumin solution, and after Cy3 (fluorescent dye) labeling, After removing low molecular weight components (washing with phosphate buffered saline (PBS)), the degree of albumin adsorption was calculated by the volume obtained by integrating the fluorescence intensities at predetermined locations on the test piece. The albumin adsorption volume of the example test piece was 249600, while the albumin adsorption volume of the control silicone rubber molded article control example test piece was 131252. In other words, it was possible to halve the protein (albumin) adsorption, which is a problem in the medical and life science fields.

(Example 14)
As a microfluidic device which is an example of the hydrophilic reinforced joined body 1, a microchemical chip shown in FIG. 7 was produced as follows. A resin mold was filled with a composition consisting of only a thermosetting liquid silicone rubber, and heat-treated at 70° C. to be thermoset, whereby a straight line having a thickness of 2 mm, a channel width of 100 μm, and a channel depth of 50 μm was formed on the lower surface. A transparent silicone rubber microchannel molded body 40 was obtained in which the liquid channel 42 and the liquid injection port 44 connected to and penetrating one end of the channel 42 were provided on the upper side surface. As in Example 6, a 0.1 mm-thick hydrophilic reinforced molding 10 having a thickness of 0.1 mm was bonded to the microchannel surface (lower surface) by molecular adhesion, and a 0.1 mm-thick support was further provided on the lower surface. The polycarbonate film which is the body 20 was joined to obtain a microchemical chip as the laminated hydrophilic strengthened joined body 1.

(Performance evaluation)
About the obtained micro chemical chip, in order to confirm the water-sending property of the laminated hydrophilic reinforced joint through the silicone rubber hydrophilic reinforced molded body example test piece 2 (hydrophilic reinforced body 2), laminated bonding was performed. When the intermediate layer of the body was subjected to a water delivery test with the comparative example molded body test piece 2-2 (liquid material alone excimer treated body 2-2), the liquid material alone excimer treated body 2-2 was laminated from the first day of production. Water could not be sent even after 10 minutes had passed since one drop of water was dropped into the opening of the joined body, but in the hydrophilicity-enhancing body 2 of the example to which the present invention is applied, external pressure is applied. Even without it, the result that water spontaneously flows in the silicone rubber microchannel was obtained, and it was confirmed that autonomous liquid transfer is possible even after 8 months or more. Further, by using a 0.1 mm thick silicone rubber hydrophilic molded sheet, it was possible to easily confirm the liquid feeding of water in the silicone rubber microchannel.

The silicone rubber hydrophilic reinforced molded body of the present invention can be used as a hydrophilic reinforced joined body to form a microfluidic device such as a microchemical chip or a cell culture device such as a culture container/culture plate. ..

The hydrophilic reinforced conjugate of the present invention is used to analyze biological components of a patient in an emergency medical field where it is necessary to promptly know the analysis result, and from traces of blood traces, body fluids, hair, biological tissue cells, etc. Extraction of DNA, PCR amplification to increase that DNA, DNA analysis to identify DNA by electrophoresis, evaluation of physical properties/efficacy of various drug candidates for new drug search, diagnosis for personalized medicine, peptides and DNA It is useful as a microchemical chip used for micro-synthesis of or functional low-molecular weight compounds. In addition, hydrophilic reinforced conjugates are attached to those analyzers and microreactors to perform various types of analysis in the medical field where genetic diagnosis and treatment are performed, in the field of criminal investigation using biological samples, and in remote areas such as oceans and lakes. It can be used for microbial search using underwater robots in Japan, and various synthesis in drug development.

Further, the hydrophilic-reinforced conjugate is used for forming cell aggregates of various cells such as adherent cells such as inducible pluripotent stem cells and embryonic stem cells, and floating cells such as hematopoietic cells, T cells and B cells. It is useful as a container/plate for cell subculture, observation, inspection, and exfoliation acquisition.

1 is a hydrophilic reinforced joined body, 10 is a hydrophilic reinforced molded body made of silicone rubber, 10a is a surface, 11a is a test solution inlet, 11b is a chemical solution inlet, 14a and 14b are outlets, 20 is a support, 20a is Surface, 21a is a test liquid injection groove, 21b is a chemical liquid injection groove, 22 is a flow path, 23a and 23b are branch flow paths, 24a and 24b are discharge grooves, 30 is a reinforcing body, and 40 is a silicone rubber micro flow path molded body. , 42 are flow paths, and 44 is a liquid injection port.

Claims (13)

The hydrophilic surface resulting from the addition of the hydrophilic group-containing compound-containing additive to the silicone rubber is a UV irradiation treated surface, an excimer UV irradiation treated surface, a corona discharge treated surface, a plasma treated surface, an electron beam irradiated treated surface, And a γ-ray-irradiated surface, which is a dry-treated surface, which is a silicone rubber hydrophilic reinforced molded product in which the surface is hydrophilically reinforced and modified ,
The hydrophilic reinforced molded article made of silicone rubber, wherein the additive containing a hydrophilic group-containing compound is a polyether-modified silicone oil . 2. The hydrophilic hydrophilic silicone rubber according to claim 1, wherein the hydrophilic group-containing compound-containing additive is the polyether-modified silicone oil composed of a silicone compound having a polyether group in a side chain of a polysiloxane skeleton. Strengthened molded body. The hydrophilic rubber-reinforced molded article according to claim 1, wherein the hydrophilic group-containing compound-containing additive has an HLB value of 3.5 to 16.9. The hydrophilic reinforcing molding of silicone rubber according to claim 1, wherein 0.1 to 30 parts by mass of the hydrophilic group-containing compound-containing additive is blended with 100 parts by mass of the silicone rubber. body. The silicone rubber is an addition-type silicone rubber, a condensation-type silicone rubber, a peroxide-crosslinking-type silicone rubber, an ultraviolet-curing-type silicone rubber, and/or a radiation-crosslinking-type silicone rubber. Hydrophilic reinforced molded product made of silicone rubber. A flat sheet, a flat plate, or a chip; a plate having irregularities on the surface; or a three-dimensional container, a culture plate having wells, a petri dish, a molded article having irregularities on the surface; Item 2. A hydrophilically strengthened molded article made of silicone rubber according to Item 1. The silicone rubber hydrophilic reinforced molded article according to claim 1, which is an autoclave sterilized silicone rubber hydrophilic reinforced molded article or a heat-treated silicone rubber hydrophilic reinforced molded article. The silicone rubber hydrophilic reinforced molded article according to claim 1, which is transparent or translucent. A step of forming a molded article having a hydrophilic surface by blending a hydrophilic group-containing compound-containing additive that is a polyether-modified silicone oil with a silicone rubber raw material component and curing the mixture.
By subjecting the surface to a dry treatment selected from a UV irradiation treatment, an excimer UV irradiation treatment, a corona discharge treatment, a plasma treatment, an electron beam irradiation treatment, and a γ-ray irradiation treatment, a silicone rubber hydrophilic reinforced molding is obtained. Method of manufacturing. The hydrophilic surface resulting from the addition of a hydrophilic group-containing compound-containing additive, which is a polyether-modified silicone oil, to silicone rubber has UV-irradiated surface, excimer UV-irradiated surface, corona discharge-treated surface, and plasma-treated surface. , A surface treated by electron beam irradiation, and a dry-treated surface selected from surfaces treated by γ-rays, whereby the hydrophilic-reinforced molded body made of silicone rubber in which the surface is hydrophilically strengthened and modified, and the support. , A hydrophilic reinforced joined body characterized by being joined. The hydrophilic reinforced joined body according to claim 10 , wherein the silicone rubber hydrophilic reinforced molded body is joined to the support at the surface thereof by the uneven surface thereof. The hydrophilic reinforced joined body according to claim 11 , which is a microfluidic device by providing the uneven surface with unevenness serving as a flow path. And the surface of the silicone rubber hydrophilic reinforced moldings, wherein the support is by covalent attachment at the adhesion by physical adsorption, and / or molecular adhesion, claim 10, characterized in that it is joined The hydrophilically strengthened joined body according to 1.

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