JP5391497B2 - Mold and method of manufacturing molded product using it - Google Patents

Description

The present invention relates to a mold having a releasable composite film formed on the surface.

In addition, the mold here refers to a high-definition mold used for molding optical parts, mechanical parts, recording media, electronic parts, biochemical chips, medical supplies, etc. that cannot use a mold release agent with accuracy. The present invention relates to a releasable mold in which a release agent that is not convenient when a release agent adheres to a product cannot be applied.

It is already well known that a chemisorbed liquid consisting of a fluorocarbon group-containing chlorosilane-based adsorbent and a non-aqueous organic solvent can be used for chemical adsorption in the liquid phase to form a monomolecular water-repellent chemisorbed film. (For example, refer to Patent Document 1).

The principle of production of a chemisorbed monolayer in such a solution is to form a monolayer using a dehydrochlorination reaction between active hydrogen such as hydroxyl groups on the substrate surface and chlorosilyl groups of chlorosilane-based adsorbents. It is in.
Japanese Patent Laid-Open No. 05-193056

Conventionally, the improvement of mold release in mold molding has been focused on the mold itself and the mold release agent. However, in mold molding that requires nano-level precision such as optical parts, the conventional shape improvement and the method of spray-coating a release agent as shown in FIG. Since the film thickness of the release agent 2 applied to the surface of the mold 1 varies by several tens to several hundreds of nanometers, an error of the mold always occurs every time of molding, which is not realistic. Furthermore, there are quite a few cases where it is inconvenient if the release agent adheres to the molded product. However, a high-definition mold that does not use a release agent has not yet been put into practical use.

On the other hand, since the conventional chemical adsorption film uses only the chemical bond between the adsorbent and the substrate surface, it is poor in wear resistance when used as it is in a mold. In addition, when a monomolecular film made of only a fluorocarbon-based material is used, there is a problem that the surface energy is too small and the flowability and penetration of the molding material are deteriorated.

In view of the above-mentioned problems, the present invention provides a mold that does not require a mold release agent and has an appropriate mold release function with controlled surface energy without damaging the processing shape of a high-definition mold and having high molding durability. Objective.

In order to achieve the above object, as shown in FIG. 1 (b), the mold of the present invention has a uniform film thickness at a nano level and a water / oil repellency fluorocarbon chemistry with controlled surface energy. The gist is to form an adsorption film on the mold surface as a release film 3. As a result, even a mold having a nanometer-level ultrafine shape is excellent in fluidity and penetration of the molded product, so that high-speed and high-precision molding can be performed. Furthermore, by forming such a release film, it is not necessary to apply a release agent, and it is possible to prevent the release agent from adhering to a molded product.

The first invention specifically provided is a mold having a highly durable releasable composite film formed on a surface thereof, wherein the coating film contains a fluorocarbon group and a hydrocarbon group (hereinafter, It is a composite film comprising a long chain substance, a short chain substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group, and a substance mainly composed of a siloxane group. It is a releasable mold.

According to a second invention, in the first invention, the molecular length of a long-chain substance mainly composed of a fluorocarbon group and a hydrocarbon group is composed mainly of a fluorocarbon group, a hydrocarbon group and a silyl group. A releasable mold characterized in that it is at least twice the molecular length of a short chain substance.

According to a third invention, in the first and second inventions, the long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group has a side chain containing the fluorocarbon group and the hydrocarbon group. A releasable mold characterized by the following.

According to a fourth aspect of the present invention, in the first to third aspects of the present invention, a short-chain material mainly composed of a fluorocarbon group and a hydrocarbon group, a short chain composed mainly of a fluorocarbon group, a hydrocarbon group, and a silyl group. A releasable mold characterized in that a chain substance is bonded and fixed to the silica film and / or the mold surface via the silyl group in a silica film made of a substance mainly composed of a siloxane group. is there.

According to a fifth aspect of the present invention, in the first to third aspects of the present invention, a long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group, a short chain composed mainly of a fluorocarbon group, a hydrocarbon group, and a silyl group. A release mold characterized in that a chain substance and a substance mainly composed of a siloxane group are bonded to each other or individually on the mold surface via a silyl group and a siloxane group, respectively.

According to a sixth invention, in the first to fifth inventions, a long-chain material mainly containing a fluorocarbon group and a hydrocarbon group, a fluorocarbon group, and a hydrocarbon group contained in the releasable composite film. Releasability characterized in that the molecular composition ratio of the short-chain substance mainly composed of silyl group and the substance mainly composed of siloxane group is 1:10:10 to 1: 0.1: 0.1 It is a mold.

A seventh invention is the mold according to any one of the first to sixth inventions, wherein a mold-release composite film is formed on the surface, and the coating film contains at least a fluorocarbon group and a hydrocarbon group as main components. A releasable mold comprising a long-chain material that has a critical surface energy of 5 to 20 mN / m.

According to an eighth invention, in the first to seventh inventions, the long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group is composed mainly of an organic fluorine-containing ether group or an organic fluorine-containing polyether group. A releasable mold characterized by being a long chain substance.

According to a ninth invention, in the first to eighth inventions, the organic fluorine-containing ether group or the organic fluorine-containing polyether group is a functional group represented by the following formula (Chemical Formula 1 or Chemical Formula 2): It is a releasable mold.

A tenth aspect of the invention is a releasable mold according to any of the first to ninth aspects, wherein the releasable composite film is formed through a silica film.

An eleventh invention is a releasable mold according to any one of the first to tenth inventions, wherein the composite film further contains a methylsilyl group.

According to a twelfth aspect of the present invention, there is provided a long-chain substance (1) having at least a fluorocarbon group and a hydrocarbon group as main components and an alkoxysilyl group, and a short chain having a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as main components. Form a releasable composite film by bringing the mold surface into contact with a composite film forming solution obtained by diluting a chain substance (2), a substance (3) mainly composed of alkoxysilyl groups, and a silanol condensation catalyst with an organic solvent. It is a manufacturing method of the mold release mold | die characterized by including the process to perform.

According to a thirteenth aspect of the present invention, there is provided a long chain substance (1) having at least a fluorocarbon group and a hydrocarbon group as main components and an alkoxysilyl group, and a short chain having a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as main components. A step of bringing a mold surface into contact with a composite film forming solution obtained by diluting a chain substance (2), a substance (3) having an alkoxysilyl group as a main component, and a silanol condensation catalyst with an organic solvent to form a film; And a step of washing or wiping off an excess solution on the surface of the mold using an organic solvent.

A fourteenth invention is the twelfth and thirteenth invention according to the twelfth and thirteenth inventions, a long-chain substance (1) comprising a fluorocarbon group and a hydrocarbon group as main components and an alkoxysilyl group, a fluorocarbon group and a hydrocarbon group, and The molecular mixing ratio of the short chain substance (2) mainly composed of alkoxysilyl groups and the substance (3) mainly composed of alkoxysilyl groups is set to 1:10:10 to 1: 0.1: 0.1 It is a manufacturing method of the mold release mold | die characterized by the above-mentioned.

According to a fifteenth aspect, in the twelfth to fourteenth aspects, the organic fluorine-containing ether group or the organic group-containing substance is used as the long chain substance (1) comprising at least a fluorocarbon group and a hydrocarbon group as main components and an alkoxysilyl group. A long-chain substance containing a fluorine polyether group and an alkoxysilyl group is used.

In a sixteenth aspect based on the fifteenth aspect, a substance represented by the following formula (Chemical Formula 3 or 4) is used as a long chain substance containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group. ,

CF ₃ — (CF ₂ ) _o — (CH ₂ ) ₂ —Si (OA) ₃ (subscript o is a short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. (AO) ₃ Si (OSi (OA) ₂ ) _p OA (p is an integer, A is an alkyl group, and OA may be Cl or NCO.) 0 or an integer, A may be an alkyl group, and OA may be Cl or NCO.)

According to a seventeenth aspect, in the fifteenth aspect, a substance represented by the following formula (Chemical Formula 5) is used as a long chain substance containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group.

CF ₃ — (CF ₂ ) _o — (CH ₂ ) ₂ —Si (OA) ₃ (subscript o is a short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. (AO) ₃ Si (OSi (OA) ₂ ) _p OA (P is 0 or an integer, A is an alkyl group) ) Is used for producing a releasable mold.

An eighteenth invention is the twelfth to seventeenth invention, in which instead of the silanol condensation catalyst, a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, an aminoalkylalkoxysilane compound, or TiO ₂ is used. It is a manufacturing method of a mold release mold characterized by using a metal oxide.

According to a nineteenth aspect, in the twelfth to seventeenth aspects, the silanol condensation catalyst includes a ketimine compound, or a metal oxide such as an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, an aminoalkylalkoxysilane compound and / or TiO _2. This is a method for producing a releasable mold characterized by using a mixture of materials.

According to a twentieth aspect of the invention, there is provided a mold release method according to any one of the twelfth to nineteenth aspects, wherein a fluorocarbon organic solvent is used as the organic solvent.

A twenty-first aspect of the invention is a method for producing a releasable mold according to the twelfth to twentieth aspects of the present invention, wherein a silica film is formed on the mold surface in advance before forming the composite film.

A twenty-second aspect of the invention is a method for producing a releasable mold according to the twelfth to twenty-first aspects of the invention, wherein the composite film is heated at 250 to 450 ° C. after the formation of the composite film.

A twenty-third aspect of the invention is a method for producing a releasable mold according to the twelfth to twenty-first aspects of the invention, wherein after the formation of the composite film, treatment is further performed with a solution in which a substance containing a methylsilyl group is dissolved. .

A twenty-fourth aspect of the invention is a molded product to which a release agent prepared using the molds of claims 1 to 11 is not attached.

More specifically, the present invention mainly comprises a long-chain substance (1) mainly comprising at least a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group, a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. The mold surface is brought into contact with a composite film forming solution obtained by diluting a short chain substance (2) as a component (2), a substance (3) containing an alkoxysilyl group as a main component and a silanol condensation catalyst with an organic solvent to release the mold. A step of forming a composite film, or a long-chain substance (1) mainly containing a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group, and a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as a main component The film is formed by contacting the surface of the mold with a composite film forming solution obtained by diluting the short chain substance (2), the substance (3) mainly composed of an alkoxysilyl group, and a silanol condensation catalyst with an organic solvent. A mold in which a highly durable releasable composite film is formed on a surface by a step of forming and a step of washing or removing an excess solution on the surface of the mold using an organic solvent, The coating comprises a long-chain material mainly composed of a fluorocarbon group and a hydrocarbon group, a short-chain material mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group, and a material mainly composed of a siloxane group. The gist of the present invention is to provide a releasable mold characterized by being a composite film.

Here, the molecular length of the long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group is set to be more than twice the molecular length of the short chain substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group. It is convenient to improve the releasability.

Further, it is convenient that the long-chain material mainly composed of a fluorocarbon group and a hydrocarbon group has a side chain containing a fluorocarbon group and a hydrocarbon group, so that the releasability can be further improved.
In addition, a long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group and a short chain substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group are composed of a substance mainly composed of a siloxane group. Bonding and fixing to the silica film and / or the mold surface through the silyl group in the silica film is advantageous in that the molding durability can be improved.

In addition, a long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group, a short chain substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group, and a substance mainly composed of a siloxane group, When they are bonded to each other or individually on the mold surface via a silyl group and a siloxane group, the molding durability can be advantageously improved.

In addition, the long-chain material mainly composed of a fluorocarbon group and a hydrocarbon group, the short-chain material mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, and a siloxane group contained in the releasable composite film. When the molecular composition ratio of the main component is 1:10:10 to 1: 0.1: 0.1, the flowability of the molded product can be controlled as well as the mold release performance, and the molding durability can be improved. It is convenient to improve.

Further, the mold is provided with a releasable composite film on the surface, and the coating contains a long chain substance mainly composed of at least a fluorocarbon group and a hydrocarbon group and has a critical surface energy of 5 When controlled to ˜20 mN / m, it is convenient to control the mold release performance as well as to control the fluidity of the molded product and to improve the molding durability.

Furthermore, if the long chain material mainly composed of a fluorocarbon group and a hydrocarbon group is a long chain material mainly composed of an organic fluorine-containing ether group or an organic fluorine-containing polyether group, molding durability can be improved. Convenient.

Further, when the organic fluorine-containing ether group or the organic fluorine-containing polyether group is a functional group represented by the following formula (Chemical Formula 1 or Chemical Formula 2), the flowability of the molded product can be controlled as well as the mold release performance. Convenient because it can improve durability.

In addition, it is advantageous that the mold-releasing composite film is formed through a silica film because the molding durability can be further improved.

Furthermore, when the composite film further contains a methylsilyl group, it is advantageous in that the flowability of the molded product can be controlled as well as the mold release performance and the molding durability can be improved. A releasable mold characterized by the following.

Further, at this time, a long-chain material (1) mainly containing a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group, and a short-chain material containing a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as main components ( If the molecular mixing ratio of 2) and the substance (3) having an alkoxysilyl group as a main component is 1:10:10 to 1: 0.1: 0.1, the mold release performance is controlled and the molded product is controlled. Conveniently, the fluidity can be controlled and the molding durability can be improved.

Further, as a long-chain substance (1) having at least a fluorocarbon group and a hydrocarbon group as main components and containing an alkoxysilyl group, a long-chain substance containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group When used, it is convenient because the mold release performance can be controlled and the molding durability can be improved.

Further, a substance represented by the following formula (Chemical Formula 3 or 4) is used as a long chain substance containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group.

CF ₃ — (CF ₂ ) _o — (CH ₂ ) ₂ —Si (OA) ₃ (subscript o is a short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. (AO) ₃ Si (OSi (OA) ₂ ) _p OA (p is an integer, A is an alkyl group, and OA may be Cl or NCO.) Use of 0 or an integer, A may be an alkyl group, and OA may be Cl or NCO. This is advantageous in that the flowability of the molded product can be controlled as well as the mold release performance and the molding durability can be improved.

In addition, as a long chain substance containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group, a substance represented by the following formula (Formula 5) is used.

CF ₃ — (CF ₂ ) _o — (CH ₂ ) ₂ —Si (OA) ₃ (subscript o is a short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. (AO) ₃ Si (OSi (OA) ₂ ) _p OA (P is 0 or an integer, A is an alkyl group) ) Is advantageous in that it can control the fluidity of the molded product as well as the mold release performance and can improve the molding durability.

Furthermore, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, an aminoalkylalkoxysilane compound, or a metal oxide such as TiO ₂ is used in place of the silanol condensation catalyst, the production time can be shortened. convenient.

In addition, when a ketimine compound, or a metal oxide such as an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, an aminoalkylalkoxysilane compound and / or TiO ₂ is mixed with the silanol condensation catalyst, the production time can be further shortened. Convenient.

Further, when a fluorocarbon organic solvent is used as the organic solvent, the film uniformity can be improved, which is convenient.
Furthermore, it is convenient to form a silica film on the mold surface in advance before forming the composite film because the density of the releasable composite film can be improved.

In addition, heating at 250 to 450 ° C. after the formation of the composite film is convenient for improving the molding durability.
Further, after forming the composite film, it is convenient to control the fluidity of the molded product by treating with a solution in which a substance containing a methylsilyl group is further dissolved.

On the other hand, a molded product produced using the mold of the present invention is convenient as a food packaging material, clothing product, or medical product because a release agent does not adhere to it.

As described above, in the releasable mold and the method for producing the same according to the present invention, a long chain substance, a fluorocarbon group, and a hydrocarbon group mainly composed of a fluorocarbon group and a hydrocarbon group are formed on the mold surface. By forming a releasable composite film containing a short-chain substance mainly composed of silyl group and a substance mainly composed of siloxane group, it has high molding durability, high moldability and penetration, and mold release. There is an effect of providing a mold satisfying the properties at the same time.

The present invention provides a mold having high molding durability, high molding fluidity and penetration, and excellent mold release properties without using a mold release agent. A long-chain substance (1) containing a hydrogen group as a main component and containing an alkoxysilyl group, a short-chain substance (2) containing a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as main components and an alkoxysilyl group as a main component To form a releasable composite film by contacting the surface of the mold with a composite film forming solution obtained by diluting the substance (3) to be condensed with a silanol condensation catalyst with an organic solvent, or a fluorocarbon group and a hydrocarbon group. A long chain substance (1) containing an alkoxysilyl group as a main component, a short chain substance (2) containing a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as main ingredients and a substance containing an alkoxysilyl group as a main component ( 3) A process of forming a film by bringing a mold surface into contact with a composite film forming solution diluted with an organic solvent and a silanol condensation catalyst to form a film, and removing or wiping off the excess solution on the mold surface with an organic solvent A mold having a highly durable releasable composite film formed on the surface thereof, wherein the coating film is a long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group, and fluorocarbon. The present invention provides a releasable mold which is a composite film containing a short chain substance mainly containing a group, a hydrocarbon group and a silyl group and a substance mainly containing a siloxane group.

According to the mold releasable mold, the drawback of being weak against the abrasion of the conventional chemical adsorption film is improved, the molding durability is excellent, and the fluidity and penetration of the molded product in the mold, and the mold release property. Has the effect of providing an excellent mold. In addition, according to the manufacturing method, an ultra-thin film having excellent film thickness uniformity can be obtained, so that it can be applied to the manufacture of molds for optical parts and the like that require nanometer level definition.

Hereinafter, details of a mold that does not require the release agent of the present invention and has excellent releasability (mold releasable mold) will be described using examples.

In the following examples, the molecular composition ratio means a molar ratio unless otherwise specified. Further, “%” not specifically mentioned means “% by weight”. In addition, this invention is not limited at all by these Examples.

First, a stainless steel mold 1 was prepared, washed thoroughly and dried. On the other hand, a substance represented by the following formula (Chemical Formula 6) is used as the substance (1) containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group.

CF ₃ — (CF ₂ ) ₇ — (CH ₂ ) ₂ —Si (OCH ₃ ) ₃ is used as the substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. Si (OCH ₃ ) ₄ is used as the substance (3) containing bismuth as the main component, and dibutyltin oxide is used as the silanol condensation catalyst, so that the amounts are 0.01, 0.01, 0.003, and 0.00005 M / L, respectively. Was then dissolved in a pentafluorobutane solvent containing 30% dichloropentafluoropropane (chlorine-containing fluorocarbon solvent) to prepare a composite film forming solution.

This composite film forming solution was immersed in the stainless steel mold 1 in normal air (relative humidity 53%, 65% in another experiment). Immediately, the excess composite film forming solution on the surface is washed away with chloroform and taken out into the air. As shown in FIG. 2, the substance 4 composed mainly of an organic fluorine-containing polyether group and a silyl group and the fluorocarbon The composition ratio of the substance 5 mainly composed of a group, a hydrocarbon group and a silyl group and the substance 6 mainly composed of a siloxane group is about 1: 1: 0.3, and the siloxane notation is between the fluorocarbon groups. A composite film 7 having a thickness of about 5 nm was formed on the surface of the stainless steel mold 1.

Here, since the stainless steel mold surface contains many hydroxyl groups of adsorbed water and natural oxide, the organic fluorine-containing ether group, or the substance containing the organic fluorine-containing polyether group and the alkoxysilyl group. The ≡Si (OCH ₃ ) group of (1), a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group (2) and a substance mainly composed of an alkoxysilyl group (3) Organic fluorine-containing fluorinated chemicals bonded to each other or to the entire surface of the mold surface by reaction of the hydroxyl groups and adsorbed water on the mold surface in the presence of a silanol condensation catalyst to dealcoholize (in this case, de-CH ₃ OH) Substances containing ether groups or organic fluorine-containing polyether groups and silyl groups as main components, substances containing fluorocarbon groups, hydrocarbon groups and silyl groups as main components and A composite film containing a substance mainly composed of a oxane group was formed on the surface of the stainless steel mold.

Since the film thickness of the composite film at this time was about nanometer, the processing accuracy of the mold was not impaired at all. In addition, the water droplet contact angle on the surface of the stainless steel mold is approximately 112 degrees (with a critical surface energy of about 8 mN / m) regardless of whether or not the cleaning process is performed. I was able to grant.

Further, since this composite film is covalently bonded to the mold surface via a siloxane bond, as shown in FIG. 3, in the wear test, after rubbed 6000 times under a load of 600 g / cm ^2. However, the water droplet contact angle could be maintained at 110 degrees or more. This condition corresponds to the condition of wiping the surface hundreds of thousands of times with fabric.

(Comparative Example 1)
For reference, in Example 1, the organic fluorine-containing ether group or the substance (1) containing the organic fluorine-containing polyether group and the alkoxysilyl group was not included, but the fluorocarbon group, the hydrocarbon group, and the alkoxysilyl group material whose main component (2) is _{CF 3 - (CF 2) 7} - (CH 2) 2 -Si (OCH 3) _3, and the material (3) composed mainly of alkoxysilyl key group Si (OCH ₃ ) ₄ , and the concentrations of the substance (2) mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group and the substance (3) mainly composed of alkoxysilyl group are 0.01 and 0, respectively. The result of the water droplet contact angle change in the abrasion resistance test of the coating when the prototype was made under the same conditions as in Example 1 except for 0.003 M / L is shown in FIG.

(Comparative Example 2)
Furthermore, in Example 1, the organic fluorine-containing ether group, or the substance (1) containing an organic fluorine-containing polyether group and an alkoxysilyl group and the substance (3) containing an alkoxysilyl group as a main component are not included. material (2) is CF ₃ composed mainly of a fluorocarbon hydrocarbon group and an alkoxysilyl group _{- (CF 2) 7 - (} CH 2) 2 -Si (OCH 3) _3, and other conditions The result of the water droplet contact angle change in the abrasion resistance test of the coating when all samples are manufactured under the same conditions as in Example 1 is shown in comparison with FIG.

From FIG. 3, except for the organic fluorine-containing ether group or the substance (1) containing the organic fluorine-containing polyether group and the alkoxysilyl group, the initial water droplet contact angle is almost the same, but the wear resistance is considerably deteriorated. I know that
Further, except for both the organic fluorine-containing ether group or the substance (1) containing an organic fluorine-containing polyether group and an alkoxysilyl group and the substance (3) mainly composed of an alkoxysilyl group, the wear resistance is further increased. It turns out that it deteriorates significantly.

Further, when the excess composite film forming solution is wiped off with a waste cloth containing ethanol, a composite film having a film thickness of about 15 nm and an initial water droplet contact angle of about 110 degrees (critical surface energy is about 8 mN / m) is formed. did it. In addition, the wear resistance at this time was not significantly different from the case of cleaning.
Further, an ethoxy group instead of a methoxy group, or a Cl or NCO group, although the reaction was different, could be formed almost similarly.

When the respective concentrations were 0.01, 0.01, 0.01, 0.00005 M / L and other conditions were the same, the composition ratio was approximately 1: 1: 1, and the film thickness was A composite film excellent in abrasion resistance having an initial water droplet contact angle of about 102 degrees (critical surface energy of about 20 mN / m) was formed at about 5 nm.

Here, the surface energy of the stainless steel mold on which the releasable composite film is formed is determined by the organic fluorine-containing ether group or the substance (1) containing the organic fluorine-containing polyether group and the alkoxysilyl group, the fluorocarbon group and the hydrocarbon. Since it substantially depends on the composition of the substance (2) mainly composed of a group and an alkoxysilyl group and the substance (3) mainly composed of an alkoxysilyl group, 1: 1: 1 to 1: 0.1: 0.1 The surface energy can be controlled to about 20 to 5 mN / m by changing the preparation composition within the range of 5 to 5 mN / m, and the fluidity and penetration of the molded product can be adjusted according to the molding material.

Further, when the composite form is formed through a film (hereinafter referred to as the silica film 8) formed in advance with a composition of 0: 0: 1 (FIG. 4), the fluorination of the composite film is performed as compared with the case without the silica film. The density of the carbon group could be improved and the wear resistance was further improved 2 to 3 times.

Here, after the composite film was formed, the wear resistance could be further improved by heating at 250 to 450 ° C. for about 30 minutes. If the heating temperature was 250 to 300 ° C., there was no problem even if heating was performed in normal air, but if it was 320 to 450 ° C., in an atmosphere substantially free of oxygen in order to prevent oxidation of the film. It was necessary to do in.

In Example 1, after the immersion reaction, the non-aqueous organic solvent is evaporated without being washed out of the solution (in this case, when the stainless steel mold is heated at 60 to 100 ° C., the solvent is evaporated. It was possible to accelerate the evaporation time, and the organic fluorine-containing ether group, or the organic fluorine-containing polyether group and the silyl group-based substance, the fluorocarbon group, the hydrocarbon group, and the silyl group. The composition ratio of the substance mainly composed of a group and the substance mainly composed of a siloxane group is approximately 1: 1: 0.3, and a composite film having a film thickness of approximately 30 nm can be formed on the surface of the stainless steel mold. It was.

Here, in the composite film forming solution, the surface of the stainless steel mold contains a large number of hydroxyl groups of adsorbed water and natural oxide, so the organic fluorine-containing ether group or the organic fluorine-containing polyether is used. ≡Si (1) of a substance (1) containing a group and an alkoxysilyl group, a substance (2) containing a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as a main component and a substance (3) containing an alkoxysilyl group as a main component OCH ₃ ) groups react with each other over the entire surface of the mold by reacting the hydroxyl groups and adsorbed water on the stainless steel mold surface in the presence of a silanol condensation catalyst to dealcoholize (in this case, de-CH ₃ OH). Organic fluorine-containing ether group chemically bonded to the surface, or organic fluorine-containing polyether group and substance mainly composed of silyl group, fluorocarbon group, hydrocarbon group and silyl A composite film containing a group-based substance and a siloxane group-based substance was formed on the stainless steel mold surface.

Furthermore, when the solvent is taken out into the air and the solvent is evaporated, the substance (1) containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group remaining on the mold surface, a fluorocarbon group and a hydrocarbon group And the substance (2) having an alkoxysilyl group as a main component and the substance (3) having an alkoxysilyl group as a main component are hydrolyzed with moisture in the air to form an organic fluorine-containing material formed on the mold surface. A composite film containing an ether group or a substance mainly composed of an organic fluorine-containing polyether group and a silyl group, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, a silyl group, and a substance mainly composed of a siloxane group. In combination with an organic fluorine-containing ether group, or an organic fluorine-containing polyether group and a silyl group as a main component, a fluorocarbon group, a hydrocarbon group, and a silyl group as a main component. That material and polymeric composite film containing a substance composed mainly of siloxane groups was formed on the stainless steel surface of the mold.

Since the film thickness of the composite film obtained at this time is on the order of several tens of nanometers, the processing accuracy of the mold is somewhat impaired, but it is at a level that does not cause any problems in molding of optical parts. In addition, the water droplet contact angle on the surface of the stainless steel mold is approximately 105 degrees (critical surface energy is about 15 mN / m) regardless of whether or not the cleaning process is performed, and has a mold release property equal to or higher than that of a Teflon (registered trademark) coat. I was able to grant.

Moreover, the abrasion test result was improved about 10 times compared with Example 1.

In Example 1, a film was produced in the same manner except for the substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group.
In this case, the composite film having a film thickness of about 5 nm including the organic fluorine-containing ether group or the organic fluorine-containing polyether group and the substance mainly composed of silyl group and the substance mainly composed of siloxane group is made of the stainless steel. Formed on the mold surface.

At this time, since the film thickness of the composite film was about nanometers, the processing accuracy of the mold was not impaired at all. In addition, the water droplet contact angle on the surface of the stainless steel mold is approximately 108 degrees (critical surface energy is about 12 mN / m) regardless of whether or not the cleaning process is performed, and has a mold release property higher than that of the Teflon (registered trademark) coat. I was able to grant.

In the abrasion test, the same results as in Example 1 were obtained.

In Example 1, a film was produced in the same manner except for the substance (3) having an alkoxysilyl group as a main component.
In this case, the film thickness of the organic fluorine-containing ether group, or the organic fluorine-containing polyether group and the substance mainly containing a silyl group, and the substance mainly containing a fluorocarbon group, a hydrocarbon group, and a silyl group are substantially reduced. A 4 nm composite film could be formed on the surface of the stainless steel mold.

At this time, since the film thickness of the composite film was still about nanometer, the processing accuracy of the mold was not impaired at all. In addition, the contact angle of water droplets on the stainless steel mold surface is approximately 114 degrees (critical surface energy is about 6 mN / m) regardless of whether or not the cleaning process is performed, which is far superior to Teflon (registered trademark) Co. It was possible to impart releasability.

In the wear test, the deterioration was somewhat faster than in Example 1, but almost the same result was obtained.

In Example 1, a film was produced in the same manner except for the substance (2) mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group and the substance (3) mainly composed of alkoxysilyl group. .

In this case, naturally, a film having a film thickness of about 3 nm made of the organic fluorine-containing ether group or the substance (1) mainly composed of the organic fluorine-containing polyether group and the silyl group could be formed on the surface of the stainless steel mold.

At this time, since the film thickness of the composite film was still about nanometer, the processing accuracy of the mold was not impaired at all. In addition, the contact angle of the water droplets on the stainless steel mold surface is approximately 116 degrees (critical surface energy is about 5 mN / m) regardless of the presence or absence of the cleaning process, which is far superior to Teflon (registered trademark) Co. It was possible to impart releasability.

In the abrasion test, although the deterioration was somewhat faster than that in Example 1, it was a coating that could be used at a practical level.
In addition, although this film was excellent in mold release property, it turned out that compared with the composite film obtained in Example 1, the molding fluidity | liquidity and penetration property in a metal mold | die will become a little worse.

Furthermore, in Example 1, a ketimine compound or a metal oxide such as TiO ₂ , an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound could be used in place of the above silanol condensation catalyst. .

For example, in place of the silanol condensation catalyst described in Example 1, the ketimine compound (H3 from Japan Epoxy Resin and Silaace S340 from Chisso was used, but the performance was almost the same). When used in concentration, the reaction time could be shortened to 30 minutes.

Furthermore, in Example 1, the above-mentioned silanol condensation catalyst and ketimine compound, or metal oxide such as TiO ₂ , organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound are used at 1: 9 to 9: When mixed with 1 and used, the reaction time could be further shortened.
Specifically, when the above-mentioned silanol condensation catalyst concentration is halved in Example 1 and the above-mentioned ketimine compound (eg, S340) is equimolarly mixed (1: 1), the reaction time is shortened to 20 minutes. did it.

In all the examples described above, as the silanol condensation catalyst, a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanate ester, and a titanate ester chelate are used. Is available. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate, and bis (acetylacetonyl) dipropyl titanate can be used.

Further, the ketimine compound that can be used is not particularly limited. For example, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3,10- Tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2, , 4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza-4,19 -There is trieicosadiene.

Further, the organic acid that can be used is not particularly limited, but there are, for example, formic acid, acetic acid, propionic acid, lactic acid, malonic acid, and the like, which have almost the same effects.

When forming a film by evaporating the solvent of the composite film forming solution, the lower the boiling point of the non-aqueous solvent used in the composite film forming solution is, the more convenient it is because it can be removed by evaporation earlier. About 50-150 degreeC was good.

On the other hand, when post-cleaning is performed, the higher the boiling point of the fluorocarbon organic solvent used in the composite film forming solution is, the more stable it is.

The fluorocarbon-based organic solvent includes a chlorofluorocarbon-based solvent, Fluorinert (product of 3M), Afludo (product of Asahi Glass), etc., and these may be used alone or mixed well. If it is a thing, you may combine 2 or more types. Furthermore, an organic chlorine solvent such as chloroform may be added. Furthermore, as an adsorbing solvent, water and alcohol (the composition ratio of water and alcohol is 2: 1 to 10: 1 by volume, and the type of alcohol is ethanol, but propanol, butanol, and ethylene glycol are also used. In the case of using a mixed solvent of 1), a silanol condensation catalyst or a co-catalyst such as ketimine cannot be used. A film could be formed.

Furthermore, as the organic solvent for washing, it is possible to use a hydrocarbon solvent that does not contain water, or a fluorocarbon solvent or a silicone solvent, and those having a boiling point of 50 to 300 ° C. are particularly suitable for use. It was suitable.

Specific examples include petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, dimethyl silicone, phenyl silicone, alkyl-modified silicone, polyether silicone, etc. Can do.

Furthermore, the following formula (Formula 3 or 4) can be used for the substance (1) containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group. Further, although the light resistance was somewhat worse, substances represented by the following formula (Chemical Formula 5) could be used, but those having an average molecular weight of about 2000 to 5000 were easy to use.

More specifically, substances represented by the following formula (Chemical Formula 7) and Formula (Chemical Formula 8) can be used.

Further, CF _3- (CF ₂ ) _o- (CH ₂ ) ₂ -Si (OA) ₃ (subscript o is used as a substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. An integer of 1 to 10, A is an alkyl group such as a methyl group or a til group.) Specifically, the following substances (1) to (18) were easy to use.

(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OCH ₃ ) ₃
(8) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) _{3
(9) CF 3 (CH 2} ) 2 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
(10) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
(13) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
(14) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OC ₂ H ₅ ) ₃
(15) (CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ ) ₂ Si (OCH ₃ ) ₂
(16) (CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ ) ₂ Si (OCH ₃ ) ₂
(17) (CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ ) ₃ SiOCH ₃
(18) (CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ ) ₃ SiOCH ₃

Furthermore, (AO) ₃ Si (OSi (OA) ₂ ) _p OA (p is 0 to 10, A is a methyl group or til alkyl group, OA as the substance (3) having an alkoxysilyl group as a main component May be Cl or NCO), but the following substances (1) to (14) are easy to use.

(1) Si (OCH ₃ ) ₄
(2) SiH (OCH ₃ ) ₃
(3) SiH ₂ (OCH ₃ ) ₂
(4) (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃
(5) Si (OC ₂ H ₅ ) ₃
(6) SiH (OC ₂ H ₅ ) ₃
(7) SiH ₂ (OC ₂ H ₅ ) ₂
(8) (H ₅ C ₂ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅
Here, m represents an integer of 1 to 6.

The conceptual diagram of the conventional metal mold | die cross section (a) and the metal mold | die cross section (b) of this invention. (A) shows the state which applied the mold release agent to the metal mold | die surface, (b) shows the state which formed the mold release monomolecular film on the metal mold | die surface.

In Example 1, the conceptual diagram which expanded the metal mold | die cross section in which the moldable composite film was formed to the molecular level.

The figure which showed the abrasion resistance test result of the mold release mold obtained in Example 1 of this invention, and the mold release mold obtained in Comparative Examples 1 and 2 by the change of a water droplet contact angle.

In Example 2, the conceptual diagram which expanded the metal mold | die cross section in which the releasable composite film was formed through the silica film to the molecular level.

DESCRIPTION OF SYMBOLS 1 Metal mold | die 2 Mold release agent apply | coated 3 Release film | membrane 4 of this invention Substance which has organic fluorine-containing ether group or organic fluorine-containing polyether group and silyl group as a main component (1)
5. Substances mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group (2)
6 Substances mainly composed of alkoxysilyl groups (3)
7 release of the composite film
8 Silica membrane

Claims (2)

A mold having a highly durable water / oil repellent / antifouling coating formed on a surface thereof, the coating comprising a fluorocarbon group and a hydrocarbon group containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group And a first substance containing a silyl group, a second substance containing a fluorocarbon group, a hydrocarbon group, and a silyl group and different from the first substance, and a third substance containing only a siloxane group A releasable mold, characterized in that the molecular length of the second substance is shorter than the molecular length of the first substance. A method for producing a molded product using the releasable mold according to claim 1.