JP7234807B2 - Water- and oil-repellent film composition and its use - Google Patents

Description

The present specification relates to a water- and oil-repellent film composition having excellent heat resistance and its use.

As materials for forming a water- and oil-repellent film capable of exhibiting antifouling properties, resin-based materials such as silicone resins and fluorine resins such as Teflon (registered trademark) and ceramic-based materials are known. Since resin-based materials are easy to process for coating, various objects to be processed can be coated with the resin-based materials. For example, cooking utensils such as ovens, appliances around stoves, parts around engine/vehicle mufflers, heaters, water heaters, etc. need to maintain antifouling properties after repeated heating.

Since the heat-resistant temperature of a film made of such a resin-based material is generally less than 300° C., its application is limited. Therefore, there is a growing demand for better heat resistance. As such a film material, for example, a three-dimensional crosslinked structure by siloxane bonds, and a material in which a hydroxyl group is capped with a methyl group at the end thereof is disclosed (Patent Document 1). This material is described as having constant water and oil repellency even after being heated at 500° C. for 24 hours.

Also disclosed is a material obtained by cross-linking a diisocyanate as a hydrophilic composition and a polysiloxane modified with amines at both ends and a polysiloxane modified with hydroxyl groups as a hydrophobic composition with a cage polysiloxane having a glycidyl group (Patent Document 2). ). It is described that this material has water and oil repellency and a decomposition temperature of about 300°C.

On the other hand, silsesquioxane having a three-dimensional crosslinked structure by siloxane bonds is known as an excellent heat-resistant material (Patent Documents 3 and 4). It is described that such silsesquioxane has a 5% weight loss rate of 1000° C. or higher.

JP 2014-185334 A JP 2015-44983 A WO2005/10077 WO2009/66608

The film disclosed in Patent Document 1 is a polysiloxane precursor obtained by polymerizing a solution containing a silane compound having a polymerizable alkoxy group and a methyl group with an acid or alkali as a catalyst at room temperature for a certain period of time. A solution is obtained by coating this precursor solution. Since it is difficult to adjust the hydrolysis reaction of the organic silane compound, a catalyst such as an acid or an alkali is essential. In addition to equipment problems such as corrosion of coating equipment, there are also safety management problems in the working environment.

In addition, in the technique of Patent Document 1, the methyl group contributes to the heat resistance and antifouling property, but the molecular weight is generally small and many alkoxy groups and silanol groups remain. Therefore, when the film is formed, the stress increases due to the condensation of these elements, resulting in a film that is easily cracked and easily peeled off, and that the film is destroyed by repeated heating. . In addition, in the coating disclosed in Patent Document 1, the contact angles of water and n-hexadecane are decreased at 400° C. or higher, and there is concern about the antifouling property at 400° C. or higher (Tables 1, 2, etc.) ).
In addition, since the film disclosed in Patent Document 2 decomposes at 300° C. or higher, it cannot be said that the heat resistance of the material itself is ensured, and it cannot be said that it has heat resistance and antifouling properties. .

Synovial properties also contribute to antifouling properties. In some cases it is important to easily dislodge these droplets from the antifouling surface as water and oil tend to slide off. In addition, such films sometimes have insufficient wear resistance.

On the other hand, Patent Documents 3 and 4 relate to polysiloxane materials having excellent heat resistance, but do not disclose water and oil repellency at all. Moreover, even those skilled in the art could not predict the water and oil repellency of these polysiloxane materials in view of their composition.

The present specification provides a water- and oil-repellent coating material excellent in usability such as film strength, antifouling property and abrasion resistance, and heat resistance, and its use.

〔式（１）において、Ｒ¹は水素原子、ヒドロシリル化反応可能な炭素－炭素不飽和結合を有する炭素原子数２～１０の有機基、及び炭素原子数１～１０のアルキル基からなる群から選択される少なくとも１種であり、Ｒ²は水素原子、ヒドロシリル化反応可能な炭素－炭素不飽和結合を有する炭素原子数２～１０の有機基、及び炭素原子数１～１０のアルキル基からなる群から選択される少なくとも１種であり（１分子中のＲ²は同一でも異なっていてもよい。）、Ｒ³は水素原子、ヒドロシリル化反応可能な炭素－炭素不飽和結合を有する炭素原子数２～１０の有機基、及び炭素原子数１～１０のアルキル基からなる群から選択される少なくとも１種であり（１分子中のＲ³は同一でも異なっていてもよい。）、Ｒ⁴は炭素原子数１～６のアルキル基であり、Ｒ²の少なくとも一部又はＲ³の少なくとも一部が、水素原子とヒドロシリル化反応可能な炭素－炭素不飽和結合を有する炭素原子数２～１０の有機基である。ｗ及びｘは正の数であり、ｖ、ｙ及びｚは、それぞれ０又は正の数であり、ｘ／（ｖ＋ｗ＋ｘ＋ｙ）は０．２以上である。〕
以下の式（２）で表される、Ｂ成分と、

〔式（２）において、Ｒ⁵及びＲ⁶は、それぞれ独立して、水酸基、炭素原子数１～３のアルキル基、炭素原子数１～３のアルコキシ基、アミノ基、エポキシ基、メルカプト基、カルボキシル基、ポリエーテル基、フェニル基、（メタ）アクリル基、カルビノール基、カルボン酸無水物基から選択される少なくとも１種であり、同一でも異なっていても良い。Ｒ⁷は、炭素数１～２０のアルキル基、フェニル基、ポリエーテル基、アラルキル基、フロロアルキル基、脂肪酸エステル基、脂肪酸アミド基から選択される少なくとも１種である。ｍは、１以上の整数であり、ｎは、1以上の整数である。〕
さらに、下記式（３）で表されるＣ成分と、

〔式（３）において、ｐ＞０、ｑ＞０、ｒ≧０、ｓ≧０、（ｐ＋２ｒ＋ｓ）＞ｑ＋ｓであり、Ｒ⁸は水素原子又は炭素原子数１～６のアルキル基である。〕
とを含有する、撥水撥油膜組成物。
［２］前記Ａ成分と前記Ｃ成分との総量に対して前記Ａ成分が５質量％以上９５質量％以下であり、
前記Ａ成分と前記Ｃ成分との総量に対して前記Ｂ成分が１質量％以上５０質量％以下である、［１］に記載の組成物。
［３］前記Ｃ成分は、重量平均分子量が２，０００以上である、［１］又は［２］に記載の組成物。
［４］前記式（１）において、（Ｒ³）₃ＳｉＯ_1/2の少なくとも一部が、Ｒ³の１つが水素原子であり他の２つが炭素原子数１～１０のアルキル基であり、少なくとも他の一部が、Ｒ³の１つがヒドロシリル化反応な炭素－炭素不飽和結合を有する炭素原子数２～１０の有機基であり、他の２つが炭素原子数１～１０のアルキル基である、［１］～［３］のいずれかに記載の組成物。
［５］前記式（１）において、前記少なくとも一部の（Ｒ³）₃ＳｉＯ_1/2のモル数をｙ１とし、前記少なくとも他の一部の（Ｒ³）₃ＳｉＯ_1/2のモル数をｙ２としたとき、（ｙ１＋ｙ２）／（ｖ＋ｗ＋ｘ＋ｙ）は０．１以上である、［４］に記載の組成物。
［６］前記（Ｒ²）₂ＳｉＯ_2/2の少なくとも一部が、Ｒ²の１つが水素原子であり他の１つが炭素原子数１～１０のアルキル基であり、少なくとも他の一部が、Ｒ²の１つがヒドロシリル化反応な炭素－炭素不飽和結合を有する炭素原子数２～１０の有機基であり他の１つが炭素原子数１～１０のアルキル基である、［１］～［５］のいずれかに記載の組成物。
［７］前記少なくとも一部の（Ｒ²）₂ＳｉＯ_2/2のモル数をｘ１とし、前記少なくとも他の一部の（Ｒ²）₂ＳｉＯ_2/2のモル数をｘ２としたとき、（ｘ１＋ｘ２）／（ｖ＋ｗ＋ｘ＋ｙ）は０．１以上である、［６］に記載の組成物。
［８］Ｒ¹は、炭素原子数１～１０のアルキル基である、［１］～［７］のいずれかに記載の組成物。
［９］ｘ／ｗは、０．８以上である、［１］～［８］のいずれかに記載の組成物。
［１０］前記Ａ成分は、水素原子とヒドロシリル化反応可能な炭素－炭素不飽和結合を有する炭素原子数２～１０の有機基とのヒドロシリル化反応に基づくＳｉ－Ｃ－Ｃ－Ｒ_ｍ－Ｓｉ（Ｒは炭素原子数１～８の有機基であり、ｍは０又は１の整数である。）が前記Ａ成分のＳｉの総モル数の０．０５以上０．３以下となるように構成されている、［１］～［９］のいずれかに記載の組成物。
［１１］前記Ａ成分において、前記ヒドロシリル化反応な炭素－炭素不飽和結合を有する炭素原子数２～１０の有機基に対して理論的に過剰の水素原子のモル数は、Ｓｉの総モル数に対して０．１以下である、［１］～［１０］のいずれかに記載の組成物。
［１２］前記Ａ成分において、少なくとも一部の前記ヒドロシリル化反応な炭素－炭素不飽和結合を有する炭素原子数２～１０の有機基と少なくとも一部の前記水素原子とによるＳｉ－Ｃ－Ｃ－Ｒ_ｍ－Ｓｉ構造（Ｒは炭素原子数１～８の有機基であり、ｍは０又は１の整数である。）を形成している、［１］～［１１］のいずれかに記載の組成物。
［１３］前記Ａ成分の数平均分子量は、５００以上２，０００以下である、［１］～［１２］のいずれかに記載の組成物。
［１４］実質的に塩酸又はアルカリを含有しない、［１］～［１３］のいずれかに記載の組成物。
［１５］ヒドロシリル化を促進する触媒を実質的に含まない、［１］～［１４］のいずれかに記載の組成物。
［１６］［１］～［１５］のいずれかに記載の組成物を基材表面に塗布し、前記組成物を加熱して硬化膜を形成する工程、
を備える、前記基材の防汚方法。
［１７］［１］～［１５］のいずれかに記載の組成物を硬化して得られる、撥水撥油膜。
［１８］ヒドロシリル化を促進する触媒を用いることなく硬化して得られる、［１７］に記載の撥水撥油膜。
［１９］加熱室と、
前記加熱室の少なくとも一部であって熱に曝露される要素表面に位置される［１７］又は［１８］に記載の撥水撥油膜と
を備える、装置。
［２０］熱に曝露される表面に位置される［１７］又は［１８］に記載の撥水撥油膜を備える、構造体。 In order to solve the above problems, the present inventors have focused on polysiloxane that is excellent in heat resistance, and have investigated various compositions of polysiloxane to evaluate film properties. The present inventors have found that by defining a certain composition of the monomers, it is possible to form a film exhibiting excellent water and oil repellency while maintaining the heat resistance of polysiloxane. Furthermore, the present inventors used a catalyst such as an acid to obtain polysiloxane, and obtained the knowledge that the siloxane precursor after polymerization with an acid can provide a water- and oil-repellent film excellent in usability and heat resistance. rice field. Furthermore, the present inventors have found that a water- and oil-repellent film having excellent usability and heat resistance can be provided by incorporating silicone oil and silicone resin into polysiloxane. This specification provides the following means based on these findings.
[1] A component siloxane compound represented by the following formula (1);

[In formula (1), R ¹ is selected from the group consisting of a hydrogen atom, an organic group having 2 to 10 carbon atoms and having a hydrosilylatable carbon-carbon unsaturated bond, and an alkyl group having 1 to 10 carbon atoms. At least one selected, and R ² consists of a hydrogen atom, an organic group of 2 to 10 carbon atoms having a hydrosilylatable carbon-carbon unsaturated bond, and an alkyl group of 1 to 10 carbon atoms. at least one selected from the group (R ² in one molecule may be the same or different), R ³ is a hydrogen atom, and the number of carbon atoms having a hydrosilylation-reactive carbon-carbon unsaturated bond is at least one selected from the group consisting of organic groups having 2 to 10 carbon atoms and alkyl groups having 1 to 10 carbon atoms (R ³ in one molecule may be the same or different), and R ⁴ is an alkyl group having 1 to 6 carbon atoms and at least part of R ² or at least part of R ³ having 2 to 10 carbon atoms having a carbon-carbon unsaturated bond capable of hydrosilylation reaction with a hydrogen atom; It is an organic group. w and x are positive numbers, v, y and z are each 0 or positive numbers, and x/(v+w+x+y) is 0.2 or more. ]
A B component represented by the following formula (2),

[In formula (2), R ⁵ and R ⁶ each independently represent a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an amino group, an epoxy group, a mercapto group, It is at least one selected from a carboxyl group, a polyether group, a phenyl group, a (meth)acryl group, a carbinol group and a carboxylic acid anhydride group, and may be the same or different. R ⁷ is at least one selected from an alkyl group having 1 to 20 carbon atoms, a phenyl group, a polyether group, an aralkyl group, a fluoroalkyl group, a fatty acid ester group and a fatty acid amide group. m is an integer of 1 or more, and n is an integer of 1 or more. ]
Furthermore, a C component represented by the following formula (3),

[In the formula (3), p>0, q>0, r≧0, s≧0, (p+2r+s)>q+s, and R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]
A water-repellent and oil-repellent film composition containing
[2] The A component is 5% by mass or more and 95% by mass or less with respect to the total amount of the A component and the C component,
The composition according to [1], wherein the B component is 1% by mass or more and 50% by mass or less with respect to the total amount of the A component and the C component.
[3] The composition according to [1] or [2], wherein the C component has a weight average molecular weight of 2,000 or more.
[4] in the above formula (1), at least part of (R ³ ) ₃ SiO _1/2 , one of R ³ being a hydrogen atom and the other two being alkyl groups having 1 to 10 carbon atoms; at least one of the other R ³ is an organic group of 2 to 10 carbon atoms having a hydrosilylation-reactive carbon-carbon unsaturated bond, and the other two are alkyl groups of 1 to 10 carbon atoms. The composition according to any one of [1] to [3].
[5] In the formula (1), y1 is the number of moles of the at least part of (R ³ ) ₃ SiO _1/2 , and the number of moles of the at least other part of (R ³ ) ₃ SiO _1/2 is y2, (y1+y2)/(v+w+x+y) is 0.1 or more.
[6] At least part of (R ² ) ₂ SiO _2/2 has one R ² being a hydrogen atom, the other being an alkyl group having 1 to 10 carbon atoms, and at least the other part being , one of R ² is an organic group having 2 to 10 carbon atoms and having a hydrosilylation-reactive carbon-carbon unsaturated bond, and the other is an alkyl group having 1 to 10 carbon atoms, [1] to [ 5].
[7] When the number of moles of the at least part of (R ² ) ₂ SiO _2/2 is x1 and the number of moles of the at least other part of (R ² ) ₂ SiO _2/2 is x2, ( The composition according to [6], wherein x1+x2)/(v+w+x+y) is 0.1 or more.
[8] The composition according to any one of [1] to [7], wherein R ¹ is an alkyl group having 1 to 10 carbon atoms.
[9] The composition according to any one of [1] to [8], wherein x/w is 0.8 or more.
[10] The component A is Si—C—C—R _m —Si based on a hydrosilylation reaction between a hydrogen atom and an organic group having 2 to 10 carbon atoms and having a carbon-carbon unsaturated bond capable of undergoing a hydrosilylation reaction. (R is an organic group having 1 to 8 carbon atoms, and m is an integer of 0 or 1.) is configured so that the total number of moles of Si in the A component is 0.05 or more and 0.3 or less The composition according to any one of [1] to [9].
[11] In the component A, the number of moles of theoretically excess hydrogen atoms with respect to the organic group having 2 to 10 carbon atoms and having a carbon-carbon unsaturated bond capable of undergoing hydrosilylation reaction is the total number of moles of Si. is 0.1 or less for the composition according to any one of [1] to [10].
[12] In the component A, at least part of the organic group having 2 to 10 carbon atoms having a hydrosilylation-reactive carbon-carbon unsaturated bond and at least part of the hydrogen atom Si—C—C— The R _m -Si structure (R is an organic group having 1 to 8 carbon atoms and m is an integer of 0 or 1). Composition.
[13] The composition according to any one of [1] to [12], wherein the A component has a number average molecular weight of 500 or more and 2,000 or less.
[14] The composition according to any one of [1] to [13], which does not substantially contain hydrochloric acid or alkali.
[15] The composition according to any one of [1] to [14], which is substantially free of a catalyst that promotes hydrosilylation.
[16] A step of applying the composition according to any one of [1] to [15] to a substrate surface and heating the composition to form a cured film;
An antifouling method for the base material, comprising:
[17] A water- and oil-repellent film obtained by curing the composition according to any one of [1] to [15].
[18] The water- and oil-repellent film according to [17], which is obtained by curing without using a catalyst that promotes hydrosilylation.
[19] a heating chamber;
and a water- and oil-repellent film according to [17] or [18] located on a surface of an element that is at least part of the heating chamber and is exposed to heat.
[20] A structure comprising the water- and oil-repellent film of [17] or [18] positioned on a surface exposed to heat.

The present disclosure discloses a water and oil repellent film composition and its use. More specifically, a water- and oil-repellent film composition, an antifouling method, a water- and oil-repellent film, and the like are disclosed. According to the present disclosure, it is possible to provide a water- and oil-repellent film having excellent water- and oil-repellency at high temperatures, good film-forming properties, and sufficient film strength to resist heating and abrasion. Furthermore, in this case, since a water- and oil-repellent film having excellent synovial properties can be provided, it has excellent water- and oil-repellency and abrasion resistance, and also has excellent water and oil removal and recovery properties. An oil-repellent film can be provided.

The present composition can exhibit properties such as, for example, excellent coating workability and ability to maintain excellent water and oil repellency even after being heated at 400° C. or higher for 24 hours.

According to the present inventors, the A component contained in the water and oil repellent film composition disclosed in the present specification (hereinafter also referred to as the present composition) is excellent in heat resistance and water and oil repellency of the film. It is thought that it has a significant contribution.

In addition, according to the present inventors, the B component lowers the surface free energy of the film, lowers the dynamic friction coefficient, and imparts synovial properties to the film surface, thereby improving water and oil repellency. considered to contribute. Improved synovial properties not only contribute to the ease of removal and recovery of adhered oil and water, but also contributes to the abrasion resistance of the film. In addition, as described below, the improvement of synovial properties by the B component is also a synergistic effect with the C component.

In addition, according to the present inventors, the C component contributes to the good film-forming properties of the composition, and also suppresses cracking and wear during and after curing, and has excellent film strength properties such as excellent toughness. found to contribute. The improvement in film strength properties contributes to the improvement of water and oil repellency per se, because it suppresses scratches and peeling of the coating film. The abrasion resistance of the film is a synergistic effect of the synovial properties of the B component in addition to the C component.

This composition exhibits a synergistic effect by containing the B component and the C component in addition to the A component. The present composition can contain the B component and the A component at the same time because the A component has compatibility with the B component and the C component, respectively. In addition, for this reason, it is possible to obtain the present composition having film-forming properties by allowing these components to be mixed during the production of the present composition. Thereby, the film obtained from the present composition can exhibit good properties of each of the A to C components.

In addition, the synovial properties exhibited by the B component and the film-forming properties and wear resistance exhibited by the C component are combined. will contribute to

As used herein, a carbon-carbon unsaturated bond means a carbon-carbon double bond or a carbon-carbon triple bond. Hereinafter, as embodiments of the present disclosure, a siloxane compound and a method for producing the same will be described, and then a water- and oil-repellent composition containing such a siloxane compound or a cured product thereof and its use will be described.

(Water- and oil-repellent film composition)
The composition can include A component, B component and C component. The present composition can adopt various aspects. The present composition can be, for example, a composition before film formation (typically in an amorphous form such as a liquid) suitable for producing a water- and oil-repellent film.

The present composition contains only the A component, the B component and the C component, and may contain other components as necessary. Other components include solvents, hydrosilylation catalysts used for curing component A, and known additives that can be added to the film-forming composition.

(A component: siloxane compound)
The siloxane compound of the present disclosure (hereinafter simply referred to as component A) is a polysiloxane having a Si—O—Si bond in its main chain skeleton. In addition, since component A has a structural unit (T unit, R ¹ -Si-O _3/2 ) having three Si-O _1/2 for siloxane bonding as an essential unit in formula (1), It is also a silsesquioxane derivative.

Component A can be represented, for example, by the following formula (1) comprising structural units (1-1), (1-2), (1-3), (1-4) and (1-5) . v, w, x, y and z in formula (1) each represent the number of moles of structural units (1-1) to (1-5). In formula (1), v, w, x, y and z mean the average ratio of the number of moles of each structural unit contained in one molecule of component A. The formula of each structural unit also shows the number of moles of the structural unit.

Each of the structural units (1-2) to (1-5) in formula (1) may be of only one type, or may be of two or more types. Moreover, the condensed form of the structural units in the actual component A is not limited to the arrangement order represented by formula (1), and is not particularly limited.

Component A has five structural units in formula (1), namely structural unit (1-1), structural unit (1-2), structural unit (1-3), structural unit (1-4) and structural unit A structural unit selected from (1-5) is a hydrogen atom (in other words, a hydrosilyl group (Si—H)) and a carbon-carbon unsaturated bond capable of hydrosilylation reaction. It can be provided in combination so as to contain 10 organic groups (hereinafter also simply referred to as unsaturated organic groups). That is, one or more structural units selected from the group consisting of the structural unit (1-2), the structural unit (1-3) and the structural unit (1-4) as structural units containing a hydrosilyl group are provided. , as a structural unit containing an unsaturated organic group, one or more selected from the group consisting of a structural unit (1-2), a structural unit (1-3) and a structural unit (1-4). can.

In addition, the A component can contain the structural unit (1-2) and the structural unit (1-3). For example, in equation (1), w and x are positive numbers and v, y and z are 0 or positive numbers.

<Constituent unit (1-1)>
This structural unit remains as represented by formula (1) and defines the Q unit as a basic structural unit of polysiloxane. The number of this structural unit in component A is not particularly limited.

<Constituent unit (1-2)>
This structural unit defines the T unit as a basic structural unit of polysiloxane. R ¹ of this structural unit is at least one selected from the group consisting of a hydrogen atom, an unsaturated organic group, and an alkyl group having 1 to 10 carbon atoms (hereinafter also referred to as unit, C _1-10 alkyl group) can be seeds. R ¹ can be, for example, an alkyl group of 1 to 10 carbon atoms rather than a hydrogen atom or an unsaturated organic group. When this structural unit does not have a group that participates in the hydrosilylation reaction, it may be possible to obtain a film having excellent high-temperature heat resistance and the like. The unsaturated organic group will be explained later.

The C _1-10 alkyl group may be either an aliphatic group or an alicyclic group, and may be linear or branched. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl groups. Such alkyl groups are, for example, straight-chain alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl groups, and also include methyl, ethyl, A linear alkyl group having 1 to 4 carbon atoms such as a propyl group and a butyl group. Another example is a methyl group.

w, which is the ratio of the number of moles of this structural unit in component A, is a positive number. Although w is not particularly limited, for example, w/(v+w+x+y) is 0.25 or more, for example, 0.3 or more, or for example, 0.35 or more. 0.4 or more. The numerical value is, for example, 0.65 or less, 0.5 or less, or, for example, 0.45 or less. By doing so, it is possible to provide the antifouling siloxane compound with excellent heat resistance. A preferable range is, for example, 0.35 or more and 0.65 or less, and for example, 0.40 or more and 0.5 or less.

The actual number of the structural units in one molecule of component A is not particularly limited, but is, for example, 1 or more and 40 or less, preferably 2 or more and 20 or less, and more preferably 3 or more. 10 or less.

<Constituent unit (1-3)>
This structural unit defines the D unit as a basic structural unit of polysiloxane. R ² of this structural unit can be at least one selected from the group consisting of a hydrogen atom, an unsaturated organic group and a C _1-10 alkyl group.

As for the C _1-10 alkyl group, the various embodiments already described can be applied to this structural unit as they are.

An unsaturated organic group is a functional group having a carbon-carbon double bond or a carbon-carbon triple bond capable of undergoing a hydrosilylation reaction with a silicon-bonded hydrogen atom (hydrosilyl group). Examples include, but are not limited to, carbon-carbon double bonds. Specific examples of such unsaturated organic groups include, but are not limited to, vinyl, orthostyryl, methstyryl, parastyryl, acryloyl, methacryloyl, acryloxy, methacryloxy, and 1-propenyl groups. , 1-butenyl group, 1-pentenyl group, 3-methyl-1-butenyl group, phenylethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-methyl-1-butynyl group, phenylbutynyl group, allyl (2-propenyl) group, octenyl (7-octen-1-yl) group, and the like. Such unsaturated organic groups are, for example, vinyl groups, parastyryl groups, allyl (2-propenyl) groups, octenyl (7-octen-1-yl) groups and also, for example, vinyl groups.

In addition, two or more unsaturated organic groups can be contained in the entire component A, and in this case, all the unsaturated organic groups may be the same or different. Also, the plurality of unsaturated organic groups may be the same and may include different unsaturated organic groups.

R ² in this structural unit may be the same or different. In addition, one or more unsaturated organic groups can be used as R ² for one or more of the structural units. One or more C _1-10 alkyl groups can be used as R ² for one or more of the structural units.

In the A component, at least some of the structural units, for example ^, both two R ² are C _1-10 alkyl groups, and for example, all the structural units are It is a C _1-10 alkyl group. In this structural unit, for example, both R ² are alkyl groups having 1 to 4 carbon atoms, and both R ² are methyl groups. By doing so, it is possible to obtain appropriate compatibility with a linear organopolysiloxane (for example, one having a dimethylpolysiloxane structure, etc.) described later.

In the A component, some of the structural units of which two R ² are both C _1-10 alkyl groups, and some of the other structural units are, for example, one of R ² is a hydrogen atom and the other is a C _1-10 alkyl group, and in some other structural units, one of R ² is an unsaturated organic group and the other is a C _1-10 alkyl group. Further, for example, both R ² of two of the present structural units of a part are C _1-10 alkyl groups, and one of R ² of the other part of the present structural units is a hydrogen atom and the other one is a C It is _{a 1-10} alkyl group, and one of the remaining structural units R ² is an unsaturated organic group and the other one is a C _1-10 alkyl group. By doing so, a Si—C—C—R _m —Si moiety (R is an organic group having 1 to 8 carbon atoms and m is an integer of 0 or 1) branched from the polysiloxane skeleton by a hydrosilylation reaction Also, R corresponds to the structural portion excluding the —C—C— bond produced by the hydrosilylation reaction of the unsaturated organic groups involved in the hydrosilylation reaction. And the heat resistance of the cured product is improved. For example, the unsaturated organic group of R ² is a vinyl group, and the branched structure is a Si--C--C--Si moiety in which m is 0.

Further, x1 is the number of moles of this structural unit in which one of R ² is a hydrogen atom and the other is a C _1-10 alkyl group, and one of R ² is an unsaturated organic group and the other is a C ₁ When the number of moles of the present structural unit that is a _-10 alkyl group is x2, (x1 + x2) / (v + w + x + y) is, for example, 0.1 or more, or, for example, 0.15 or more, or, for example, 0 .18 or higher. Further, the numerical value is, for example, 0.4 or less, or, for example, 0.3 or less, or, for example, 0.25 or less. A preferable range is, for example, 0.1 or more and 0.4 or less, or for example, 0.18 or more and 0.25 or less.

x, which is the ratio of the number of moles of this structural unit in component A, is a positive number. x is not particularly limited. 0.4 or more. The numerical value is, for example, less than 0.5 and, for example, 0.45 or less. This is because if the molar number x is large, the antifouling property is improved, but if it is too large, the heat resistance is lowered. A suitable range is, for example, 0.2 or more and less than 0.5, and for example, 0.3 or more and 0.45 or less.

Further, x relates to the relationship with w of the structural unit (1-2) described above. 7 or more, for example 0.8 or more, for example 0.9 or more, for example 1.4 or less, for example 1.2 or less, or for example 1. 1 or less. This is because a favorable balance between the heat resistance and the antifouling property can be achieved by doing so. A preferable range is, for example, 0.2 or more and 1.4 or less, or for example, 0.7 or more and 1.2 or less.

The actual number of the structural units in one molecule of component A is not particularly limited, but is, for example, 1 or more and 40 or less, preferably 2 or more and 20 or less, and more preferably 3 or more. 10 or less.

<Constituent unit (1-4)>
This structural unit defines the M unit as a basic structural unit of polysiloxane. R ³ of this structural unit can be at least one selected from the group consisting of a hydrogen atom, an unsaturated organic group and a C _1-10 alkyl group.

Regarding the unsaturated organic group and the C _1-10 alkyl group, the various aspects already described can be applied to this structural unit as they are.

R ³ in this structural unit may be the same or different. Also, one or more unsaturated organic groups can be used as R ³ for one or more of the structural units. One or more C _1-10 alkyl groups can be used as R ³ for one or more of the structural units.

In component A, only this structural unit may have a hydrogen atom capable of hydrosilylation reaction and an unsaturated organic group, or only the structural unit (1-3) described above may be hydrosilylated. may be provided with a hydrogen atom and an unsaturated organic group, and both the present structural unit and the structural unit (1-3) are provided with a hydrogen atom capable of hydrosilylation reaction and an unsaturated organic group good too.

In the A component, at least some of the main structural units are, for example, two R ³ are both C _1-10 alkyl groups and the other R ³ is a hydrogen atom or an unsaturated organic group.

In the A component, some of the structural units have one R ³ is a hydrogen atom, the other two R ³ are both C _1-10 alkyl groups, and some other structural units have one R ³ is an unsaturated organic group, and the other two R ³ are both C _1-10 alkyl groups. Further, for example, one R ³ is a hydrogen atom in some of the present structural units, both of the other two R ³ are C _1-10 alkyl groups, and all other present structural units are one R ³ is an unsaturated organic group and the other two R ³ are both C _1-10 alkyl groups. By doing so, a Si—C—C—R _m —Si portion (R is an organic group having 1 to 8 carbon atoms and m is an integer of 0 or 1 is formed in the linear portion of the polysiloxane skeleton. ) can be formed, and the heat resistance is improved. For example, the unsaturated organic group of R ³ is a vinyl group, and the branched structure is a Si--C--C--Si moiety in which m is 0.

In addition, y1 is the number of moles of this structural unit in which one of R ³ is a hydrogen atom and the other two are C _1-10 alkyl groups, and one of R ³ is an unsaturated organic group and the other two are C ₁ When y2 is the number of moles of the structural unit that is a ₋₁₀ alkyl group, (y1+y2)/(v+w+x+y) is, for example, 0.1 or more, or, for example, 0.15 or more, or, for example, 0.15 or more. 18 or more. Further, the numerical value is, for example, 0.4 or less, or, for example, 0.3 or less, or, for example, 0.25 or less. A preferable range is, for example, 0.1 or more and 0.4 or less, or for example, 0.18 or more and 0.25 or less.

y, which is the ratio of the number of moles of this structural unit in component A, is 0 or a positive number. If the structural unit (1-2) does not have a hydrogen atom and/or an unsaturated organic group, y will be a positive number. Although y is not particularly limited, for example, y/(v+w+x+y) is 0.1 or more, for example 0.15 or more, or for example 0.18 or more. The numerical value is, for example, 0.4 or less, or, for example, 0.3 or less, or, for example, 0.25 or less. By doing so, it is possible to achieve both appropriate cross-linking reactivity and heat resistance. A preferable range is, for example, 0.1 or more and 0.4 or less, or for example, 0.18 or more and 0.25 or less.

The actual number of the structural units in one molecule of component A is not particularly limited, but is, for example, 0 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more. 5 or less.

<Constituent unit (1-5)>
This structural unit defines a unit containing an alkoxy group or a hydroxyl group in the A component. That is, R ⁴ in this structural unit is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group may be either an aliphatic group or an alicyclic group, and may be linear or branched. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl and hexyl groups. Typically, alkyl groups having 2 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, etc. and, for example, an alkyl group having 1 to 6 carbon atoms.

The alkoxy group in this structural unit is an "alkoxy group" which is a hydrolyzable group contained in the raw material monomer to be described later, or an alcohol contained in the reaction solvent substituted the hydrolyzable group of the raw material monomer. It is an "alkoxy group" that remains in the molecule without hydrolysis or polycondensation. In addition, the hydroxyl group in this structural unit is, for example, a hydroxyl group remaining in the molecule without polycondensation after the "alkoxy group" is hydrolyzed.

z, which is the ratio of the number of moles of this structural unit in component A, is 0 or a positive number. The number of this structural unit in one actual molecule of component A is not particularly limited, but is, for example, 0 to 5, preferably 0 to 3, and more preferably 0 or more. 2 or less.

(Number of moles of hydrosilyl groups and unsaturated organic groups in component A)
Component A is one or more structural units selected from the above three structural units (1-2) to (1-4), and comprises a hydrosilyl group and an unsaturated organic group. can be done. For example, the combination of structural units having these groups is one or two selected from structural unit (1-3) and structural unit (1-4).

In component A, for example, a Si—C—C—R _m —Si constituent moiety (R is an organic group having 1 to 8 carbon atoms and m is is an integer of 0 or 1) is 0.05 or more and 0.3 or less of the total number of moles of Si in component A, ie, (v+w+x+y). Further, for example, it is 0.05 or more and 0.25 or less, for example, it is 0.07 or more and 0.25 or less, or for example, it is 0.08 or more and 0.2 or less. This is because a good balance between curability and antifouling properties can be achieved by doing so. The number of moles of the Si—C—C—R _m —Si constituent moiety based on the hydrosilylation reaction between the hydrosilyl group and the unsaturated organic group is such that the hydrosilyl group and the unsaturated organic group in component A are completely 1: This is a theoretical value obtained by assuming that the reaction was performed at 1. Any excess of either the hydrosilyl group or the unsaturated organic group is calculated based on the lesser group. A crosslinked structure based on a hydrosilylation reaction is, for example, a Si—C—C—Si structure in which the unsaturated organic group is a vinyl group and m in the structure is 0.

In component A, the number of moles of hydrosilyl groups (hydrogen atoms) theoretically in excess with respect to the unsaturated organic groups is, for example, 0.3 or less relative to the total number of moles of Si. It is 25 or less, or, for example, 0.2 or less, or, for example, 0.15 or less, or, for example, 0.1 or less. This is because if there are too many excessive hydrosilyl groups, they are likely to be oxidized during heating, resulting in the generation of OH groups that reduce the antifouling property. A preferable range is, for example, 0.05 or more and 0.4 or less, and for example, 0.07 or more and 0.3 or less. This tendency is considered to be remarkable when excessive hydrosilyl groups are included in the T structure. That is, when excessive hydrosilyl groups are present in the T structure, the oxidized hydrosilyl groups tend to remain as Si—OH groups due to steric hindrance derived from the T structure. On the other hand, when excessive hydrosilyl groups are present in the D structure and the M structure, it can be said that the oxidized hydrosilyl groups tend to undergo dehydration condensation and form siloxane bonds. Therefore, in component A, it is preferable that the number of hydrosilyl groups with a T structure as a structural unit is as small as possible, and is configured to be 0.2 or less, for example, 0.1 or less, relative to the total number of moles of Si. For example, it is 0.05 or less, and it is 0, for example. By doing so, it is possible to provide a balance between heat resistance and antifouling properties.

<Molecular weight etc.>
The number average molecular weight of component A is preferably in the range of 300 to 10,000. Such component A itself has low viscosity and is easily dissolved in an organic solvent, the viscosity of the solution is easy to handle, and the storage stability is excellent. Considering coatability, storage stability, heat resistance, spray coatability, etc., the number average molecular weight is preferably 300 to 8,000, more preferably 300 to 6,000, more preferably 300 to 3,000. , and preferably 300 to 2,000, more preferably 500 to 2,000. Considering spin coatability and storage stability, it is, for example, 500 to 1,500, and considering heat resistance and spray coatability, it is, for example, 1,000 to 2,000. The number-average molecular weight can be determined by GPC (gel permeation chromatography), for example, using polystyrene as a standard substance under the measurement conditions in [Examples] described later.

Component A is liquid and preferably has a viscosity at 25°C of 30,000 mPa s or less, more preferably 10,000 mPa s or less, and further preferably 5,000 mPa s or less. It is preferably 3,000 mPa·s or less, particularly preferably 1,000 mPa·s or less. Furthermore, it is preferably 100 mPa·s or less. However, the lower limit of the above viscosity is usually 1 mPa·s.

The A component described above is a novel polysiloxane per se, and can be defined more specifically by, for example, one or more of (1) to (4) shown below.
(1) at least part of (R ³ ) ₃ SiO _1/2 , one of R ³ is a hydrogen atom and the other two are alkyl groups having 1 to 10 carbon atoms, and at least the other part is One of R ³ is an organic group of 2 to 10 carbon atoms having a hydrosilylation-reactive carbon-carbon unsaturated bond, and the other two are alkyl groups of 1 to 10 carbon atoms.
(2) When the number of moles of the at least part of (R ³ ) ₃ SiO _1/2 is y1 and the number of moles of the at least other part of (R ³ ) ₃ SiO _1/2 is y2, ( y1+y2)/(v+w+x+y) is 0.1 or more.
(3) at least part of (R ² ) ₂ SiO _2/2 , one of R ² is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms, and at least the other part is One of R ² is an organic group of 2 to 10 carbon atoms having a hydrosilylation-reactive carbon-carbon unsaturated bond, and the other is an alkyl group of 1 to 10 carbon atoms.
(4) When the number of moles of at least a portion of (R ² ) ₂ SiO _2/2 is x1 and the number of moles of the at least other portion of (R ² ) ₂ SiO _2/2 is x2, (x1+x2 )/(v+w+x+y) is 0.1 or more.

<Method for producing component A>
A component can be manufactured by a well-known method. The method for producing the A component is disclosed in WO 2005/010077, WO 2009/066608, WO 2013/099909, JP 2011-052170, JP 2013-147659, etc. It is disclosed in detail as a method for producing siloxanes.

A component can be manufactured with the following method, for example. That is, the method for producing component A can comprise a condensation step of performing a hydrolysis/polycondensation reaction of raw material monomers to give the structural unit of formula (1) by condensation in an appropriate reaction solvent. In this condensation step, a silicon compound having four siloxane bond forming groups (hereinafter referred to as "Q monomer"), which forms the structural unit (1-1), and the structural unit (1-2) are formed. A silicon compound having three siloxane bond-forming groups (hereinafter referred to as "T monomer") and a silicon compound having two siloxane bond-forming groups forming the structural unit (1-3) (hereinafter referred to as "D monomer" ) and a silicon compound (hereinafter referred to as “M monomer”) that forms a structural unit (1-4) having one siloxane bond-forming group.

In this specification, specifically, a Q monomer that forms the structural unit (1-1), a T monomer that forms the structural unit (1-2), and a D monomer that forms the structural unit (1-3) And, of the M monomers forming the structural unit (1-4), at least the T monomer and the D monomer are used. It is preferable to include a distillation step of distilling off the reaction solvent, by-products, residual monomers, water, etc. in the reaction solution after hydrolysis and polycondensation reaction of the raw material monomers in the presence of the reaction solvent.

The siloxane bond forming group contained in the Q monomer, T monomer, D monomer, or M monomer that is the raw material monomer is a hydroxyl group or a hydrolyzable group. Among these, hydrolyzable groups include a halogeno group and an alkoxy group. At least one of Q monomer, T monomer, D monomer and M monomer preferably has a hydrolyzable group. The hydrolyzable group is preferably an alkoxy group, more preferably an alkoxy group having 1 to 4 carbon atoms, because it has good hydrolyzability and does not produce an acid by-product in the condensation step.

In the condensation step, the siloxane bond forming group of the Q monomer, T monomer or D monomer corresponding to each structural unit is preferably an alkoxy group, and the siloxane bond forming group contained in the M monomer is preferably an alkoxy group or a siloxy group. . Monomers corresponding to each structural unit may be used alone, or two or more of them may be used in combination.

Examples of the Q monomer that gives the structural unit (1-1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like. Examples of T monomers that give the structural unit (1-2) include trimethoxysilane, triethoxysilane, tripropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane. silane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, trichlorosilane and the like. Examples of T monomers that give the structural unit (1-2) include trimethoxyvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, trimethoxyallylsilane, triethoxyallylsilane, trimethoxy(7-octen-1-yl)silane. , (p-styryl)trimethoxysilane, (p-styryl)triethoxysilane, (3-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane, (3-acryloyloxypropyl)trimethoxy silane, (3-acryloyloxypropyl)triethoxysilane, and the like. Examples of the D monomer that gives the structural unit (1-3) include dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, dimethoxybenzylmethylsilane, diethoxybenzyl methylsilane, dichlorodimethylsilane, dimethoxymethylsilane, dimethoxymethylvinylsilane, diethoxymethylsilane, diethoxymethylvinylsilane and the like. The M monomer that gives the structural unit (1-4) includes hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, 1,1,3,3 that gives two structural units (1-4) by hydrolysis. -tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, methoxydimethylsilane, ethoxydimethylsilane, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, as well as methoxytrimethylsilane, ethoxytrimethylsilane , methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorodimethylsilane, chlorodimethylvinylsilane, chlorotrimethylsilane, dimethylsilanol, dimethylvinylsilanol, trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, and the like. Organic compounds that give the structural unit (1-5) include 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, methanol, ethanol and the like. of alcohol. According to the above description, compositions containing such monomers to obtain the A component are also provided. Such a composition is suitably used as a siloxane compound for use in water- and oil-repellent films.

Alcohol can be used as a reaction solvent in the condensation step. Alcohol is a narrowly defined alcohol represented by the general formula R--OH, and is a compound having no functional groups other than an alcoholic hydroxyl group. Specific examples include, but are not limited to, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, 2-pentanol, 3-pentanol, 2-methyl -2-butanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pentane Examples include tanol, 3-methyl-3-pentanol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, cyclohexanol and the like. Among these, isopropyl alcohol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol, Secondary alcohols such as cyclohexanol are used. In the condensation step, these alcohols can be used singly or in combination of two or more. More preferred alcohols are compounds capable of dissolving the required concentration of water in the condensation step. Alcohols with such properties are compounds having a water solubility of 10 g or more per 100 g of alcohol at 20°C.

The alcohol used in the condensation step, including the additional input during the hydrolysis / polycondensation reaction, is used in an amount of 0.5% by mass or more with respect to the total amount of all reaction solvents, thereby gelling the generated component A. can be suppressed. The amount used is preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 40% by mass or less.

The reaction solvent used in the condensation step may be alcohol alone, or may be a mixed solvent with at least one sub-solvent. The co-solvent may be either a polar solvent, a non-polar solvent, or a combination of both. Preferred polar solvents are secondary or tertiary alcohols having 3 or 7 to 10 carbon atoms, diols having 2 to 20 carbon atoms, and the like. When a primary alcohol is used as a co-solvent, it is preferably used in an amount of 5% by mass or less of the total reaction solvent. A preferred polar solvent is 2-propanol, which is commercially available at low cost, and is selected from 2-propanol, secondary alcohols having 4 to 6 carbon atoms and tertiary alcohols having 4 to 6 carbon atoms. By using alcohol together, even if these alcohols cannot dissolve the water at the concentration required in the hydrolysis step, the required amount of water can be dissolved together with the polar solvent, and gelation can be suppressed. . A preferable amount of the polar solvent is 20 parts by weight or less, more preferably 1 to 20 parts by weight, particularly preferably 3 to 10 parts by weight, based on 1 part by weight of the alcohol according to the present invention.

Non-polar solvents include, but are not limited to, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, alcohols, ethers, amides, ketones, esters, cellosolve, and the like. . Among these, aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons are preferred. Such a non-polar solvent is not particularly limited, but for example, n-hexane, isohexane, cyclohexane, heptane, toluene, xylene, methylene chloride, etc. are preferable because they azeotrope with water, and when these compounds are used together, After the condensation step, when the reaction solvent is removed from the reaction mixture containing the A component by distillation, water and a polymerization catalyst such as an acid dissolved in water can be efficiently distilled off. As the non-polar solvent, xylene, which is an aromatic hydrocarbon, is particularly preferred because it has a relatively high boiling point. The amount of the non-polar solvent used is 50 parts by mass or less, more preferably 1 to 30 parts by mass, particularly preferably 5 to 20 parts by mass, per 1 part by mass of the alcohol according to the present invention.

The hydrolysis/polycondensation reaction in the condensation step proceeds in the presence of water. The amount of water used for hydrolyzing the hydrolyzable groups contained in the raw material monomer is preferably 0.5 to 5 mol, more preferably 1 to 2 mol, relative to the hydrolyzable groups. Moreover, the hydrolysis/polycondensation reaction of the raw material monomer may be carried out without a catalyst, or may be carried out using a catalyst. An acid or an alkali is used as a catalyst in the hydrolysis/polycondensation reaction. As such catalysts, acid catalysts exemplified by, for example, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid; and organic acids such as formic acid, acetic acid, oxalic acid and p-toluenesulfonic acid are preferably used. The amount of the acid catalyst used is preferably an amount corresponding to 0.01 to 20 mol%, and an amount corresponding to 0.1 to 10 mol%, relative to the total amount of silicon atoms contained in the raw material monomer. It is more preferable to have

Completion of the hydrolysis/polycondensation reaction in the condensation step can be appropriately detected by the methods described in the above-mentioned various publications. In addition, in the condensation step of manufacturing the A component, an auxiliary agent can be added to the reaction system. Examples thereof include antifoaming agents for suppressing foaming of the reaction solution, scale control agents for preventing scale deposition on reaction vessels and stirring shafts, polymerization inhibitors, hydrosilylation reaction inhibitors, and the like. The amount of these auxiliaries to be used is arbitrary, but is preferably about 1 to 100% by mass relative to the concentration of component A in the reaction mixture.

After the condensation step in the production of component A, by providing a distillation step for distilling off the reaction solvent and by-products, residual monomers, water, etc. contained in the reaction solution obtained from the condensation step, the stability of the generated component A and usability can be improved. In particular, by using a solvent azeotropic with water as the reaction solvent and simultaneously distilling off, the acid or base used as the polymerization catalyst can be efficiently removed. For the distillation, depending on the boiling point of the solvent used, etc., a temperature of 100° C. or lower and reduced pressure conditions can be used as appropriate.

(B component: linear organopolysiloxane)
The composition can include a B component. As the B component, for example, linear organopolysiloxane exhibiting an oily state, which is sometimes referred to as a so-called silicone oil, can be used. By blending the B component with the A component, more excellent water and oil repellency can be exhibited. Although it is speculation and does not restrict the present disclosure theoretically, it is believed that the "combination" of the B component reduces the surface free energy of the film of the present composition and, as a result, improves the water and oil repellency. Conceivable.

The B component is represented, for example, by the following formula (2).

Component B is represented by formula (2), where R ⁵ and R ⁶ are each independently a hydrogen atom, a hydroxy group, an alkyl group having about 1 to 3 carbon atoms, or a It can be an alkoxy group, an unsaturated organic group, and the like. Preferred are hydrogen atoms, hydroxy groups, alkoxy groups, and unsaturated organic groups capable of cross-linking with component A. Alkyl groups that do not crosslink with the A component also function effectively, but hydrogen atoms and unsaturated organic groups are crosslinked by hydrosilylation (addition) reactions, and hydroxy groups and alkoxy groups are crosslinked by dehydration and dealcoholization (condensation) reactions. Expected to be heat resistant and antifouling. That is, it is preferable to have a reactive group that reacts with a hydrosilyl group or an alkoxysilyl group of the A component at either or both ends of the B component. Various aspects already described can be applied to the unsaturated organic group. In addition, although it is sufficient if at least one or both ends have these reactive groups, it is not excluded that side chains have these reactive groups.

R ⁷ is at least one selected from an alkyl group having 1 to 20 carbon atoms, a phenyl group, a polyether group, an aralkyl group, a fluoroalkyl group, a fatty acid ester group and a fatty acid amide group, and is, for example, a methyl group. be. m is, for example, an integer of 10 or more, or an integer of 30 or more, for example. Also, m is an integer of 500 or less, or an integer of 120 or less, for example.

The polystyrene equivalent weight average molecular weight of component B measured by gel permeation chromatography is, for example, 1,000 to 50,000, and for example, 2,000 to 30,000. When the molecular weight of the B component is small, it is easily compatible with the siloxane compound, and the transparency of the film is relatively high. Conversely, when the molecular weight of the B component is large, the film tends to separate from the siloxane compound and become opaque, but the water repellency and oil repellency tend to improve, probably because the B component is oriented on the surface.

The B component used in the present composition can be appropriately selected in consideration of, for example, the compatibility with the C component described later, the synovial properties to be exhibited by the B component, and the water and oil repellency of the present composition at high temperatures. can.

Such B components can be synthesized by known methods by using alkoxy or halogenyl silane compounds selected to have the structures described.

Component B includes, for example, silanol-modified dimethylpolysiloxane at both ends with a weight average molecular weight of 1,000 to 50,000, vinyl-modified dimethylpolysiloxane at both ends with a weight average molecular weight of 1,000 to 50,000, and the like. be done. Examples of such B components include XC96-723, YF3800, XF3905, XF40-A1987 (manufactured by Momentive Performance Materials Japan Co., Ltd.), KF-9701, X-21-5841 (Shin-Etsu Chemical Co., Ltd. Co., Ltd.), DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-V21, DMS-V22, DMS-V25, DMS-V31, DMS-V33, DMS-V35 (manufactured by Gelest Co., Ltd.) and the like.

The present composition can be used by blending component B in an amount of about 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of component A, for example. Further, for example, it can be used at 5 parts by mass or more and 25 parts by mass or less, or for example, 10 parts by mass or more and 25 parts by mass or less.

When the present composition contains the B component and the C component, the B component can be contained in any amount with respect to the total mass of the A component and the C component. For example, it is 0.1% by mass or more and 50% by mass or less. If it is less than 0.1% by mass, it is likely to be difficult to obtain the effect as an antifouling aid or synovial additive, and if it exceeds 50% by mass, the siloxane compound or branched organopolysiloxane has relatively high film-forming properties. This is because the ratio of the B component, which is difficult to form a film, is too large, resulting in insufficient coating film formation, which tends to lead to a decrease in heat resistance and antifouling properties and abrasion resistance. Further, for example, it is 1% by mass or more and 40% by mass or less, and for example, it is 10% by mass or more and 30% by mass or less.

(C component: branched organopolysiloxane)
The composition can further contain a C component. The C component is represented by Formula (3), for example. Branched organopolysiloxanes are sometimes referred to as so-called silicone resins, for example.

Component C is represented by formula (3), where R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and may be the same or different. R ⁹ preferably contains a hydrogen atom. In this case, the C component becomes a dehydration condensation type, and can be cured by heating at 150° C. or higher to cause a dehydration condensation reaction without requiring a hydrosilylation reaction catalyst.

R ⁸ can typically be an alkyl group of 1 to 4 carbon atoms. Alkyl groups may be linear or branched. Examples of R ⁸ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.

p and q in formula (3) can be p>0 and q>0, respectively. That is, the T unit can be an essential component in the C component. This can contribute to the hardness and toughness of the film. Also, for example, p and q can simultaneously satisfy p>0 and q>0. This can further contribute to both the hardness and toughness of the film. Also, r and s in equation (3) can be r≧0 and s≧0, respectively. Also, for example, r and s can simultaneously satisfy r≧0 and s≧0. That is, the D unit in the C component can be an optional component, and even with only the T unit, it is possible to exhibit the film strength characteristics.

In addition, in Equation (3), p+2r+s>q+s can be established. That is, the total number of methyl groups on T units and D units in the C component can be greater than the total number of phenyl groups on T units and D units. By setting the C component to such a configuration, both good film hardness and toughness can be achieved.

The weight average molecular weight of the C component can be, for example, 2,000 or more. This is because if the weight-average molecular weight is too small, the crosslink density becomes too high, which causes cracks and peeling. again. For example, it is 3,000 or more. On the other hand, in the present composition, the upper limit of the weight molecular weight of the C component may be appropriately determined by examining the film properties to be obtained as necessary and determining applicability. Although not particularly limited, for example, 2 million or less, for example, 1 million or less, for example, 500,000 or less, for example, 20,000 or less, or for example, 10,000 or less and, for example, 8,000 or less. The weight average molecular weight can be obtained as a polystyrene equivalent weight average molecular weight using gel permeation chromatography.

When the present composition contains the B component and the C component, the C component can be contained in any amount with respect to the total mass of the A component and the B component. For example, it is 5% by mass or more and 95% by mass or less. This is because if the amount is less than 5% by mass, wear resistance tends to decrease, and if it exceeds 95% by mass, heat resistance and antifouling properties tend to decrease. Further, for example, it is 10% by mass or more and 90% by mass or less, 10% by mass or more and 80% by mass or less, or, for example, 10% by mass or more and 70% by mass or less.

Component C can be synthesized by using an alkoxy or halogenylsilane compound selected to have the structure described, according to a known method, for example, the method for producing component A already described.

Examples of the C component include organopolysiloxanes having a methyl group and a phenyl group. Examples of such C components include KR112, KR211, KR212, KR255, KR271, KR272, KR282, KR300, KR311 (manufactured by Shin-Etsu Chemical Co., Ltd.), RSN0249, 220FLAKE, 233FLAKE, 249FLAKE, 804RESIN, 805RESIN, 806RESIN. 840RESIN (manufactured by Dow Toray Co., Ltd.) and the like.

(solvent)
The composition can be diluted with a solvent as necessary and used for film formation. The solvent is preferably a solvent that dissolves component A, and when component B and/or component C are included, a solvent that dissolves these additional components is preferred. Examples thereof include aliphatic hydrocarbon solvents and aromatic hydrocarbons. Examples include various organic solvents such as solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, and cellosolve solvents. In the presence of a hydrosilylation catalyst such as Pt, a solvent other than alcohol is preferred in order to avoid decomposition of the Si—H group.

(hydrosilylation catalyst)
The composition may also contain a hydrosilylation catalyst. A hydrosilylation catalyst can promote the hydrosilylation reaction of the A component. Examples of hydrosilylation catalysts include simple substances of group 8 to group 10 metals such as cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum, organometallic complexes, metal salts and metal oxides. A platinum-based catalyst is usually used. Examples of platinum-based catalysts include cis-PtCl ₂ (PhCN) ₂ , platinum carbon, platinum complexes coordinated with 1,3-divinyltetramethyldisiloxane (Pt(dvs)), platinum vinylmethyl cyclic siloxane complexes, platinum carbonyl- Vinylmethyl cyclic siloxane complex, tris(dibenzylideneacetone)diplatinum, chloroplatinic acid, bis(ethylene)tetrachlorodiplatinum, cyclooctadienedichloroplatinum, bis(cyclooctadiene)platinum, bis(dimethylphenylphosphine)dichloroplatinum , tetrakis(triphenylphosphine)platinum, and the like. Among these, platinum complexes coordinated with 1,3-divinyltetramethyldisiloxane (Pt(dvs)), platinum vinylmethyl cyclic siloxane complexes, and platinum carbonyl-vinylmethyl cyclic siloxane complexes are particularly preferred. In addition, Ph represents a phenyl group. The amount of catalyst used is preferably 0.1 mass ppm or more and 1000 mass ppm or less, more preferably 0.5 to 100 mass ppm, and 1 to 50 mass ppm with respect to the amount of component A. It is even more preferable to have

When the present composition contains a catalyst for hydrosilylation reaction, the hydrosilylation reaction may take precedence over dehydration polycondensation of the residual alkoxy group or hydroxyl group in the structural unit (1-5) in component A, While having a hydrosilylated structure portion, the alkoxy group or hydroxyl group may be provided so as to allow further cross-linking reaction.

When the present composition contains a hydrosilylation catalyst, a hydrosilylation reaction inhibitor may be added to suppress gelation of component A and improve storage stability. Examples of hydrosilylation inhibitors include methylvinylcyclotetrasiloxane, acetylene alcohols, siloxane-modified acetylene alcohols, hydroperoxides, and hydrosilylation inhibitors containing nitrogen, sulfur or phosphorus atoms. .

The present composition may be a composition for film formation or may be substantially free of a hydrosilylation catalyst. As will be described later, the A component can be cured by heat treatment to accelerate the hydrosilylation reaction even in the absence of a hydrosilylation catalyst. In addition, when the film is formed without containing the hydrosilylation catalyst, the water and oil repellency of the film may be improved. In the present composition, "substantially free of a hydrosilylation catalyst" means that the hydrosilylation catalyst is not intentionally added, and that the content of the hydrosilylation catalyst relative to the amount of the A component is, for example, 0.5. It is less than 1 ppm by mass, or for example 0.05 ppm by mass or less.

Although the present composition may contain the polymerization catalyst used in synthesizing the components A to C, it is preferred that the composition does not substantially contain the polymerization catalyst. This is because if a polymerization catalyst is contained, its liquid properties (acidic or alkaline) may cause corrosion of various facilities and equipment for coating, etc., and there is concern that the safety of the working environment may decrease. . After the hydrolysis/polycondensation for obtaining the A component, the polymerization catalyst can be reduced to such an extent that it can be said to be substantially free by distilling off the water and the volatile solvent. For example, the amount of the polymerization catalyst in the present composition is, for example, 0.1% by mass or less, or, for example, 0.05% by mass or less, or, for example, 0.01% by mass or less, or, for example, 0.005% by mass. % or less. Incidentally, the quantitative determination of the polymerization catalyst can be carried out, for example, by Cl- ion chromatography.

(other ingredients)
Various additives may be further added to the present composition when it is subjected to curing. Examples of additives include reactive diluents such as tetraalkoxysilanes and trialkoxysilanes (trialkoxysilanes, trialkoxyvinylsilanes, etc.). These additives are used within a range that does not impair the heat resistance of the obtained cured product of component A.

<Method for producing a film using the present composition>
A film having excellent water and oil repellency can be formed by supplying the present composition to the surface of an object to be processed having an arbitrary shape and curing the composition. For example, the composition can be applied to the surface of the site where water and oil repellency is required, and then the composition can be cured. In this composition, since the A component is a liquid substance with a viscosity of 30000 mPa s or less at 25 ° C., this composition can also maintain a similar liquid state, and during curing, the surface of the workpiece is It can be applied as it is.

The supply of the present composition to the surface of the object to be processed is not particularly limited, but for example, ordinary coating methods such as spray coating, casting, spin coating and bar coating can be used.

The present composition generally comprises formation of a crosslinked structure (primary curing) by polycondensation reaction of residual alkoxy groups and/or hydroxyl groups in components A, B and C, and hydrosilyl groups in component A and unsaturated organic groups. A cured product of the present composition can be obtained by either or both of the formation of a crosslinked structure (secondary curing) by the hydrosilylation reaction of . The cured product of the present composition is generally a cured product consisting of only primary curing or a cured product containing both primary and secondary curing. Characterized.

<Curing method of the present composition, curing method mainly for primary curing>
In the present composition, in order to obtain a primary cured product by promoting polycondensation of unreacted alkoxy groups and silanol groups of components A, B and C (hereinafter also referred to as component A), for example, component A can be heated at a temperature from 50° C. to 200° C. in the absence of a hydrosilylation catalyst. Alternatively, for example, heating may be performed at a temperature of 100° C. or higher and 150° C. or lower in the absence of a hydrosilylation catalyst. In the temperature range of 50° C. or higher and 200° C. or lower, the curing temperature may be constant, or a combination of temperature rise and/or temperature drop may be used. At a temperature of 50° C. or higher and 200° C. or lower, a crosslinked structure can be formed mainly by the reaction (hydrolysis/polycondensation reaction) of alkoxysilyl groups. Under these heating conditions, a crosslinked structure may be partially formed by the hydrosilylation reaction even in the absence of a hydrosilylation reaction catalyst.

In the case of primary curing at a temperature of 50° C. or higher and 200° C. or lower, the initial curing time is usually 0.1 to 10 hours, preferably 0.5 to 5 hours.

<Curing Method of the Present Composition, Curing Method Mainly for Secondary Curing>
The secondary cured product of the present composition is obtained, for example, by reacting the present composition in the presence of a hydrosilylation catalyst at a relatively low temperature (for example, room temperature to 200° C. or less, preferably 50° C. to 150° C.). can be obtained by In this case, since the hydrosilylation reaction is accelerated rather than the polycondensation reaction of the A component and the like, primary curing also proceeds, but alkoxy groups and the like tend to remain. The curing time when using a hydrosilylation catalyst is usually 0.05 to 24 hours, preferably 0.1 to 5 hours.

The secondary cured product of the present composition may also be, for example, the present composition in the absence of a hydrosilylation catalyst after primary curing at 200°C or less, or without such primary curing, for example, above 200°C to 400°C. It can be obtained by heating at a temperature of ° C. or lower. By secondary curing under such conditions, for example, even if the film thickness after curing is 0.1 μm or more and 1 μm or less, excellent water and oil repellency can be obtained at high temperatures. If the temperature is 400° C. or lower, unreacted hydrosilyl groups tend to remain, but water and liquid repellency at high temperatures may be excellent. The heating temperature is also, for example, 350° C. or lower, and is, for example, 300° C. or lower. It should be noted that it is not excluded to carry out the secondary curing at a temperature higher than 400° C., for example, the secondary curing can be carried out at 600° C. or lower, or for example, 500° C. or lower.

When the secondary curing is promoted by heat in the absence of a hydrosilylation catalyst, the heating temperature may be gradually increased in multiple stages. Also, the heating time at each temperature is, for example, 0.1 to 2 hours, or, for example, 0.1 to 1 hour, or, for example, 0.2 to 0.5 hours. Typically, after 10 minutes at 200° C., the temperature can be increased to 350° C. for 10 minutes, and so on. In order to raise the heating temperature, for example, the temperature can be raised at a rate of about 5 to 10° C./min.

The curing of the present composition, including primary curing and secondary curing such as component A, may be performed in the air or in an inert gas atmosphere such as nitrogen gas, regardless of the presence or absence of a catalyst. may be carried out under reduced pressure. However, in order to promote the reaction of the alkoxysilyl groups present in component A, etc., the atmosphere preferably contains water to the extent that the alkoxysilyl groups can be hydrolyzed. In the air, the moisture contained in the air promotes the hydrolysis reaction of the alkoxysilyl groups, and the hydrosilyl groups are oxidized by oxygen to form hydroxysilyl groups, so sufficient curing can proceed. . On the other hand, in an inert gas atmosphere or under reduced pressure, it is less susceptible to changes in volume due to oxidation, so that a cured product with few cracks can be obtained. As another method for producing a cured product of the present composition, it is preferable to carry out primary curing in the air and secondary curing in the air, in an inert gas atmosphere such as nitrogen gas, or under reduced pressure.

In addition, the present composition may contain a solvent as described above. If a solvent is included, it is preferred to remove the solvent prior to curing. Removal of the solvent may be done in air, in an inert gas atmosphere, or under reduced pressure. Heating may be used to remove the solvent, but the heating temperature in that case is preferably less than 200°C, more preferably 50°C or higher and 150°C or lower. Although the time required for distilling off the solvent is not particularly limited, it can be, for example, about 0.1 to 0.5 hours. Incidentally, the removal of such a solvent may be accompanied by primary curing and secondary curing.

The present composition becomes a film-like body formed on the surface of the object to be processed by the method for producing a film described above. The cured product of the present composition includes, for example, the A component and the cured products of the A component, the B component and the C component. As such a cured product, the unreacted alkoxy groups in component A, etc., that is, the alkoxy groups and hydroxyl groups of R ⁴ in the structural unit (1-5) are dehydrated and polycondensed to sufficiently form siloxane bonds, resulting in further cross-linking. A cured product obtained by curing by accelerating (curing by polycondensation of such residual alkoxy groups is also referred to as primary curing) is exemplified.

In addition, other cured products are cured by causing a hydrosilylation reaction between the hydrogen atoms and unsaturated organic groups provided in the structural units (1-2) to (1-3) to further promote cross-linking. (Such curing is also referred to as secondary curing.) Cured products are exemplified. Such a cured product (hereinafter also referred to as a secondary cured product) is formed by hydrosilylation reaction of at least a part of the functional groups (hydrosilyl groups and unsaturated organic groups) that undergo hydrosilylation reaction in these structural units of component A. Structural moieties (-Si-C-C-R _m -Si-, -Si-C=C-R _m -Si -) (also referred to as hydrosilylation structural moieties, where R is an organic group of 1 to 8 carbon atoms and m is an integer of 0 or 1). Examples thereof include -Si-C-C-Si- and -Si-C=C-Si- moieties.

For example, when the present composition contains a component B in addition to the A component, in addition to the above cured product of the A component, a cured product obtained by polycondensation of the B component, or a product obtained by polycondensation of the A component and the B component May contain hardened material.

Further, for example, when the present composition contains component C in addition to component A, in addition to the above cured product of component A, a cured product obtained by polycondensation of hydroxyl groups or alkoxy groups of branched organopolysiloxane and component A and branched organopolysiloxane. Further, for example, when A component, B component and C component are included, in addition to the A component, each cured product and the cured products of each component are included.

When the composition is film-formed, the composition is generally a secondary cured product. The hydrosilylated structural part can contribute to practical film strength and film performance.

In the case of a film-like body cured from the present composition, the film thickness is not particularly limited, but can be, for example, 0.05 μm to 10 μm. Further, for example, it is 0.1 μm or more and 3 μm or less, for example, it is 0.2 μm or more and 2 μm or less, or for example, it is 0.2 μm or more and 1.5 μm or less.

The primary cure of the A component may be accompanied by a secondary cure, and the secondary cure may be accompanied by a primary cure, and the secondary cure is often accompanied by a primary cure. Therefore, the cured product of the present composition is generally a secondary cured product, often accompanied by primary curing. A typical cured product is characterized by the presence or absence of a crosslinked structure due to secondary curing. The cured product is detected by, for example, ¹ H NMR, ²⁹ Si NMR, Q units, T units, D units and M units, structural units such as alkoxy groups, and structural regularity (irregularity), and IR The composition and structure can be specified by detecting the characteristic group by spectrum.

For example, the heat resistance of the present composition containing the secondary cured product of component A can be evaluated using a simultaneous differential thermogravimetric analyzer (TG/DTA) or the like. A cured product of the present composition obtained by curing the present composition without using a hydrosilylation reaction catalyst can have a weight loss rate of about 5% at 1000° C. and exhibits high heat resistance. Also, even if a catalyst for hydrosilylation reaction is used, the weight reduction rate of the cured product at 1000° C. can be about 10% by adjusting the amount of the catalyst, etc., showing high heat resistance.

Further, for example, the water/oil repellency of the present composition containing the secondary cured product of component A can be evaluated using a contact angle meter. For example, using a contact angle meter equipped with a video recording function, 4 μm of water or oleic acid is dropped on the coating film surface of the present composition, and the water repellency or oil repellency is evaluated based on the contact angle 10 seconds after dropping. can. In addition, the coating film is an enamel, stainless steel, or glass test piece having a plane of 5 cm × 5 cm to 15 cm × 15 cm (typically, 1 cm × 5 cm), and the film thickness with respect to the plane It is formed at 1 μm. The contact angle is measured at 5 different points that are roughly evenly distributed on the coating film, and the average value of the 3 points excluding the maximum and minimum values is evaluated. The present composition has a contact angle of, for example, 40° or more, for example, 45° or more, or, for example, 50° or more when oleic acid is dropped after 24 hours at 400°C.

(Heat resistant antifouling method)
The heat resistant antifouling method disclosed herein can comprise the steps of applying the present composition to a substrate surface and heating the composition to form a cured product. According to this method, it is possible to impart heat resistance to the surface of the base material and form a film having excellent water and oil repellency at high temperatures. This method can be implemented not only as a method for manufacturing a device having a heating chamber, which will be described later, but also as a repair method for maintaining or improving the antifouling property of such devices.

The material of the substrate is not particularly limited, but examples thereof include metal materials such as stainless steel, ceramic materials, and glass materials such as enamel. The substrate, which is the object to be processed, is not particularly limited, but includes, for example, elements of equipment having a heating chamber such as the cooking equipment described below, and structures exposed to heat in factory equipment. Examples of the method of applying the present composition to the substrate surface include the already explained spray coating. Further, the curing of the A component in the present composition can be carried out under the various conditions already explained according to the application, but preferably a method intended for secondary curing can be employed.

<Apparatus equipped with heating chamber and manufacturing method thereof>
The device disclosed in the present specification (hereinafter also simply referred to as the device) comprises a heating chamber and a film-like composition of the present invention provided on the surface of an element that is at least part of the heating chamber and is exposed to heat. can be provided with According to the apparatus, the element of the heating chamber can be provided with the composition as a film, so that the element can be imparted with water and oil repellency and antifouling properties. Since this composition is excellent in water and oil repellency at high temperatures, even when the inside of the heating chamber is heated to a high temperature of about 300°C, the antifouling property of elements such as the inner wall is ensured, and the object to be heated is For example, it is difficult to attach dirt such as oil, etc., and it is easy to remove dirt.

Examples of this device include various cooking devices including an electric or gas heating chamber, such as an oven device used in a kitchen, a grill device attached to a gas cooker, and the like. Heating devices for industrial use, such as factory equipment, are also included. It should be noted that, particularly in industrial applications, the heating chamber may be a tunnel oven or the like. In such devices, the composition is provided as a film on the element exposed to heat, such as the inner wall. Gas, liquid, and solid generated from the object to be heated are likely to adhere to the inner wall as it is heated. In addition to the inner wall of the heating chamber, the element exposed to heat may be, for example, other elements to which substances generated from the object to be heated may adhere during heating. Examples thereof include the bottom of the heating chamber, the inner wall of the opening/closing portion of the heating chamber, the top plate placed in the heating chamber, and a member for placing or holding an object to be heated such as a net. Although such elements are not particularly limited, they are made of, for example, metallic materials such as stainless steel, ceramic materials, glass materials such as enamel, and the like.

On the element surface of such a heating chamber, the present composition is provided as a film, for example, with a film thickness as already described. The composition preferably includes a cured product with a secondary cure having hydrosilylated structural moieties. Moreover, it is preferably a cured product obtained by secondary curing in the absence of a hydrosilylation catalyst. Furthermore, it preferably contains linear organopolysiloxane.

For example, in the manufacturing process of the device, or in a manufacturing process separate from the manufacturing of the device, the composition is supplied to the surface of an element such as an inner wall, cured, and the composition is applied to the surface of the element. It can be manufactured by a method including forming a water- and oil-repellent film on the object. The composition can be applied to the element by a conventional coating method such as, but not limited to, spray coating, casting, spin coating, bar coating and the like. In addition, the curing of component A in the present composition can be performed under the various conditions already described, but preferably a method intended for secondary curing can be employed.

<Structure and its manufacturing method>
This specification also provides constructions comprising the composition on the surface of an element exposed to heat. Such structures can be various installations in factories or the like, or parts thereof, or building elements that make up the factory. According to such a structure, as with the heating chamber, it is possible to impart water and oil repellency and impart excellent antifouling properties. Such structures include, for example, industrial machinery, machine tools, ducts for exhaust air, etc., scrubbers, etc., and their materials are also varied, as are the elements of the heating chamber.

Various embodiments including the film thickness of the present composition on the surface of such a structure, the cured form, and the method of forming a film of the present composition include the application of the present composition to the surface of an element exposed to heat in the heating chamber described above. Various embodiments of the article can be employed.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is by no means limited to this example. In addition, "Mn" and "Mw" mean the number average molecular weight and the weight average molecular weight, respectively, by gel permeation chromatography (hereinafter abbreviated as "GPC") in a toluene solvent at 40 ° C. GPC columns "TSK gel G4000HX" and "TSK gel G2000HX" (model name, manufactured by Tosoh Corporation) were used for separation, and the molecular weight was calculated from the retention time using standard polystyrene. In the ¹ H-NMR analysis of the obtained A component, the sample was dissolved in deuterated chloroform and measured and analyzed. Furthermore, the viscosity of the obtained component A was measured at 25°C using an E-type viscometer.

(Synthesis of A component (polysiloxane P1))
A four-necked flask was equipped with a magnetic stirrer, a dropping funnel, a reflux condenser and a thermometer, and the inside of the flask was made into a nitrogen gas atmosphere. The flask was then charged with a magnetic stirrer, 142.64 g (0.8 mol) of methyltriethoxysilane, 96.18 g (0.8 mol) of dimethoxydimethylsilane, and 13.43 g of 1,1,3,3-tetramethyldisiloxane. (0.1 mol), 18.64 g (0.1 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 138.11 g of 2-butanol and 414.33 g of xylene, and While stirring the contents at 25° C., a mixture of 74.86 g of a 3.74% by mass hydrochloric acid aqueous solution and 69.06 g of 2-butanol was added dropwise from the dropping funnel over 1 hour to initiate a hydrolysis/polycondensation reaction. did After the dropwise addition was completed, the reaction solution was allowed to stand at 25° C. for 18 hours. Then, volatile components including water are distilled off from the reaction solution under reduced pressure (temperature: 11° C. to 60° C., pressure: 52 to 1 mmHg) to obtain a colorless liquid (hereinafter referred to as “polysiloxane (P1)”) 142. .2 g was obtained. The number average molecular weight (Mn) of this polysiloxane (P1) was measured by GPC and found to be 580, and the weight average molecular weight (Mw) was 830. Also, the viscosity at 25° C. was measured with an E-type viscometer and found to be 11 mPa·s. As a result of 1H-NMR analysis, most of the raw materials reacted quantitatively. The content of alkoxy groups (R ⁸ O _1/2 ) was 8.0 wt %, and the molar ratio of alkoxy groups to total Si was 0.064. .

Table 1 also shows the molar ratio of raw materials used in the synthesis of polysiloxane P1, and the molar ratio of Si, hydrosilyl H, and vinyl groups of unsaturated organic groups contained in the raw materials used. In addition, Table 2 shows Si derived from raw materials, Si—H groups, Si—H groups derived from triethoxysilane, Si—H groups/Si (molar ratio), triethoxy silane-derived Si—H groups/Si (where the molar ratio is However, the molar ratio), Si-C-C-Si/Si (the molar ratio), (X1 + X2) / (v + w + x + y), (y1 + y2) / (v + w + x + y), w / (v + w + x + y) and y / (v + w + x + y), etc. , each molar amount based on the charged amount and each molar amount based on the results of 1H-NMR analysis are shown.

(Synthesis of A component (polysiloxane P2))
According to the composition shown in Table 1 below, the raw materials are used in a molar amount that is 1/10 of the molar ratio shown for the raw materials shown in Table 1, and isopropyl alcohol is used as the solvent, in the same manner as polysiloxane P1. Polysiloxane P2 was obtained. Table 2 shows the respective molar amounts of these polysiloxanes. Further, when the number average molecular weight (Mn) was measured by GPC, it was 1,250, and the weight average molecular weight (Mw) was 2,960. Moreover, when the viscosity at 25° C. was measured with an E-type viscometer, it was 37 mPa·s.

In addition, polysiloxanes P3 to P4 were obtained in the same manner as polysiloxane P1, except that raw materials were used in a molar amount that was 1/10 of the molar ratio shown for the raw materials shown in Table 1, and isopropyl alcohol was used as the solvent. Table 2 shows the respective molar amounts of these polysiloxanes. Further, the number average molecular weights (Mn) were measured to be 1110 and 1440, respectively, and the weight average molecular weights (Mw) were 1290 and 1990, respectively. Also, the viscosities at 25° C. were measured with an E-type viscometer and found to be 14 and 43 mPa·s, respectively.

As a result of 1H-NMR analysis, most of the raw materials reacted quantitatively. , the contents of alkoxy groups are 0.03, 0.9 and 0.9 wt%, respectively, and the molar ratios of alkoxy groups to total Si are 0.018, 0.010 and 0.010, respectively. there were. Table 2 shows the composition ratio of each Si—H group, etc. of P2 to P4 in the same manner as P1.

In addition to using the polysiloxanes P1 and P2 synthesized in Example 1 as the A component (siloxane compound), the B component (straight-chain organopolysiloxane) and the C component (branched organopolysiloxane) were used with the compositions shown in Table 3. was used to prepare a film-forming composition of an example. That is, a solvent was added to the A component to dissolve the A component, then the B component was added and dissolved, and then the C component was added and sufficiently stirred to obtain the film-forming compositions of Examples 1A to 18A. In addition, film-forming compositions of Comparative Examples 1A to 19A were also prepared.

（１）シリコーンオイルＡ：
両末端シラノール変性シリコーンオイル、Ｍｎ８６００、Ｍｗ２２０００
（２）シリコーンオイルＢ：
両末端シラノール変性シリコーンオイル、Ｍｎ１８００、Ｍｗ４０００
（３）シリコーンレジンＡ：
Ｔ単位からなる、脱水縮合型メチルフェニルシリコーンレジン（Ｍｗ７、５００）
（４）シリコーンレジンＢ：
Ｔ単位及びＤ単位からなる、脱水縮合型メチルフェニルシリコーンレジン（Ｍｗ３、０００）
（５）シリコーンレジンＣ：
Ｔ単位及びＤ単位からなる、脱水縮合型メチルシリコーンレジン（Ｍｗ１、７９０、０００）
（６）シリコーンレジンＤ：
Ｔ単位、Ｄ単位及びＭ単位からなる、付加重合型メチルフェニルシリコーンレジン（Ｍｗ２、８２０）
（７）シリコーンレジンＥ：
Ｔ単位、Ｄ単位及びＭ単位からなる、付加重合型メチルフェニルシリコーンレジン（Ｍｗ１、６４０）
（８）シリコーンレジンＦ：
Ｔ単位、Ｄ単位及びＭ単位からなる、脱水縮合型メチルフェニルシリコーンレジン（Ｍｗ１、４００）
（９）シリコーンレジンＧ：
Ｔ単位からなる、付加重合型プロピルフェニルシリコーンレジン（Ｍｗ２、０００）
（１０）ＭＥＫ：
メチルエチルケトン

(1) Silicone oil A:
Both terminal silanol-modified silicone oil, Mn8600, Mw22000
(2) Silicone oil B:
Both terminal silanol-modified silicone oil, Mn1800, Mw4000
(3) Silicone resin A:
Dehydration-condensation type methylphenyl silicone resin (Mw 7,500) consisting of T units
(4) Silicone resin B:
Dehydration condensation type methylphenyl silicone resin (Mw 3,000) consisting of T units and D units
(5) Silicone resin C:
Dehydration condensation type methyl silicone resin (Mw 1,790,000) consisting of T units and D units
(6) Silicone resin D:
Addition polymerization type methylphenyl silicone resin (Mw2, 820) consisting of T units, D units and M units
(7) Silicone resin E:
Addition polymerization type methylphenyl silicone resin (Mw1, 640) consisting of T units, D units and M units
(8) Silicone resin F:
Dehydration condensation type methylphenyl silicone resin (Mw1, 400) consisting of T units, D units and M units
(9) Silicone resin G:
Addition polymerization type propylphenyl silicone resin (Mw 2,000) consisting of T units
(10) MEK:
methyl ethyl ketone

Various film-forming compositions prepared in this way are applied to the surface of a 10 cm × 10 cm enamel and stainless steel (SUS304) test piece as a substrate by spin coating (600 rpm for 5 seconds) and dried at 50 ° C. for 5 minutes. After distilling off the solvent, after heating at 200 ° C. for 10 minutes, the temperature was raised for 15 minutes and heated at 350 ° C. for 10 minutes to cure each composition, and the film thickness shown in Tables 4 and 5. A membrane was obtained.

The contact angles (°) of the films on these specimens were measured after returning to room temperature after curing (initial) and after heating at 400° C. for 24 hours. The contact angle was measured by dropping 4 μl of water and/or the same amount of oleic acid using a contact angle meter (manufactured by Eiko Seiki Co., Ltd.) equipped with a moving image recording function, and measuring the droplet 10 seconds after dropping. The contact angle was measured at 5 evenly arranged measurement points for each test piece, and the average value of the 3 points excluding the maximum and minimum values was taken as the measured value.

Furthermore, a 500 g load is applied to BEMCOT M-3II (manufactured by Asahi Kasei Co., Ltd.), and the film after curing is subjected to abrasion treatment by reciprocating a predetermined number of times (1000 times). and measured. Furthermore, the state of the film after the abrasion treatment (presence or absence of scratches or peeling, peeling rate: %) was observed using a laser microscope VK-9700 manufactured by Keyence.

The results are shown in Tables 4 and 5. In Table 5, in the examples in which two types of film thicknesses are described by dividing them by slashes, the film having the film thickness on the left side of the slashes was subjected to the abrasion treatment to evaluate the abrasion resistance.

As shown in Tables 4 and 5, by containing the A component, the B component, and the C component, the surface of enamel and stainless steel can exhibit excellent water and oil repellency even after heating at 400 ° C. for 24 hours. rice field. In addition, even after the abrasion treatment, the film maintained a sufficient film state without being peeled off. As a result, it was found that this film can exhibit sufficient water and oil repellency even after the abrasion treatment.

On the other hand, in the comparative examples, it was found that the composition could not be prepared without the B component, but that the heat-resistant antifouling property tended to deteriorate even if the B component was too much. Moreover, it was found that when the C component was not contained, sufficient wear resistance could not be obtained. From the above, it was found that the inclusion of the A component, the B component and the C component can simultaneously satisfy the heat resistance and antifouling property and the wear resistance on the enamel and stainless steel surfaces. Furthermore, when the C component is a dehydration condensation type having a methyl group and a phenyl group and is a silicone resin consisting of only T units and only T units and D units as structural units, it has heat and stain resistance on enamel and stainless steel surfaces. And it was found that a film excellent in abrasion resistance can be obtained.

Furthermore, it will be shown that the disclosure of the present specification can be applied to the polysiloxanes P3 to P4 synthesized in Examples as the A component in the same manner as P1 to P2.

In addition to using the synthesized polysiloxanes P1 to P4 as the A component, the composition shown in Table 6 was used as the B component to prepare film-forming compositions of Examples. That is, 0.5 g of each of polysiloxanes P1 to P4 is taken, and as a solvent, the final resin (polysiloxane and silicone oil) fraction specified in Table 6 (NV: the mass ratio of the resin to the total mass of the resin and solvent ( %)), and various silicone oils are added at the mass ratio shown in Table 5 below (P: Si (polysiloxane: silicone oil) = 5: 1, etc.). They were mixed to form various film-forming compositions. These compositions were applied by spin coating (at 600 rpm for 5 seconds and further at 1500 rpm for 8 seconds) on the surfaces of enamel, stainless steel (SUS304) and glass test pieces of approximately 10 cm x 10 cm as substrates, and then at 50°C. After drying for 5 minutes to evaporate the solvent, heating at 200 ° C. for 10 minutes, heating for 15 minutes and heating at 350 ° C. for 10 minutes to cure each composition, the film thickness shown in Table 5. A membrane was obtained. With respect to these films, the contact angles of water and oleic acid after curing (initial stage) and after heat treatment (400° C., 24 hours) were evaluated according to the examples. Results are shown in Table 6.

As shown in Table 6, polysiloxanes P1 to P4, even in compositions that do not contain a silicone resin, which is the C component, all have similarly good heat and stain resistance on the surfaces of various substrates. have understood. Therefore, it was found that the present composition comprising the polysiloxanes P1 to P4 as the A component and further comprising the B component and the C component can exhibit excellent heat resistance and antifouling properties and abrasion resistance.

Claims (20)

A component siloxane compound represented by the following formula (1);

[In formula (1), R ¹ is selected from the group consisting of a hydrogen atom, an organic group having 2 to 10 carbon atoms and having a hydrosilylatable carbon-carbon unsaturated bond, and an alkyl group having 1 to 10 carbon atoms. At least one selected, and R ² consists of a hydrogen atom, an organic group of 2 to 10 carbon atoms having a hydrosilylatable carbon-carbon unsaturated bond, and an alkyl group of 1 to 10 carbon atoms. at least one selected from the group (R ² in one molecule may be the same or different), R ³ is a hydrogen atom, and the number of carbon atoms having a hydrosilylation-reactive carbon-carbon unsaturated bond is at least one selected from the group consisting of organic groups having 2 to 10 carbon atoms and alkyl groups having 1 to 10 carbon atoms (R ³ in one molecule may be the same or different), and R ⁴ is an alkyl group having 1 to 6 carbon atoms and at least part of R ² or at least part of R ³ having 2 to 10 carbon atoms having a carbon-carbon unsaturated bond capable of hydrosilylation reaction with a hydrogen atom; It is an organic group. w and x are positive numbers, v, y and z are each 0 or positive numbers, and x/(v+w+x+y) is 0.2 or more. ]
A B component represented by the following formula (2),

[In formula (2), R ⁵ and R ⁶ each independently represent a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an amino group, an epoxy group, a mercapto group, It is at least one selected from a carboxyl group, a polyether group, a phenyl group, a (meth)acryl group, a carbinol group and a carboxylic acid anhydride group, and may be the same or different. R ⁷ is at least one selected from an alkyl group having 1 to 20 carbon atoms, a phenyl group, a polyether group, an aralkyl group, a fluoroalkyl group, a fatty acid ester group and a fatty acid amide group. m is an integer of 1 or more, and n is an integer of 1 or more. ]
Furthermore, a C component represented by the following formula (3),

[In the formula (3), p>0, q>0, r≧0, s≧0, (p+2r+s)>q+s, and R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]
A water-repellent and oil-repellent film composition containing The A component is 5% by mass or more and 95% by mass or less with respect to the total amount of the A component and the C component,
The composition according to claim 1, wherein said B component is 1% by mass or more and 50% by mass or less relative to the total amount of said A component and said C component. The composition according to claim 1 or 2, wherein the C component has a weight average molecular weight of 2,000 or more. In the above formula (1), at least part of (R ³ ) ₃ SiO _1/2 is such that one of R ³ is a hydrogen atom and the other two are alkyl groups having 1 to 10 carbon atoms, and at least other Some claim that one of R ³ is an organic group of 2 to 10 carbon atoms having a hydrosilylation-reactive carbon-carbon unsaturated bond and the other two are alkyl groups of 1 to 10 carbon atoms. Item 4. The composition according to any one of items 1 to 3. In the formula (1), the number of moles of the at least part of (R ³ ) ₃ SiO _1/2 is y1, and the number of moles of the at least other part of (R ³ ) ₃ SiO _1/2 is y2. 5. The composition according to claim 4, wherein (y1+y2)/(v+w+x+y) is 0.1 or more when . At least part of (R ² ) ₂ SiO _2/2 has one R ² being a hydrogen atom and the other being an alkyl group having 1 to 10 carbon atoms, and at least another part being R ² any one of claims 1 to 5, wherein one of is an organic group having 2 to 10 carbon atoms having a hydrosilylation-reactive carbon-carbon unsaturated bond and the other is an alkyl group having 1 to 10 carbon atoms. The composition according to . When the number of moles of the at least part of (R ² ) ₂ SiO _2/2 is x1 and the number of moles of the at least other part of (R ² ) ₂ SiO _2/2 is x2, (x1+x2)/ 7. The composition of claim 6, wherein (v+w+x+y) is 0.1 or greater. A composition according to any preceding claim, wherein R ¹ is an alkyl group of 1 to 10 carbon atoms. A composition according to any preceding claim, wherein x/w is greater than or equal to 0.8. The A component is Si—C—C—R _m —Si (R is is an organic group having 1 to 8 carbon atoms, and m is an integer of 0 or 1.) is configured so that the total number of moles of Si in the A component is 0.05 or more and 0.3 or less. , a composition according to any one of claims 1-9. In the component A, the number of moles of theoretically excess hydrogen atoms with respect to the organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated bond capable of hydrosilylation reaction is based on the total number of moles of Si. The composition according to any one of claims 1 to 10, which is 0.1 or less. In the component A, Si—C—C—R _m — composed of at least a portion of the organic group having 2 to 10 carbon atoms and having a hydrosilylation-reactive carbon-carbon unsaturated bond and at least a portion of the hydrogen atoms The composition according to any one of claims 1 to 11, which forms a Si structure (R is an organic group having 1 to 8 carbon atoms and m is an integer of 0 or 1). The composition according to any one of claims 1 to 12, wherein the A component has a number average molecular weight of 500 or more and 2,000 or less. A composition according to any one of claims 1 to 13, which is substantially free of hydrochloric acid or alkali. A composition according to any preceding claim which is substantially free of catalysts that promote hydrosilylation. A step of applying the composition according to any one of claims 1 to 15 to a substrate surface and heating the composition to form a cured film,
An antifouling method for the base material, comprising: A water- and oil-repellent film obtained by curing the composition according to any one of claims 1 to 15. 18. The water- and oil-repellent film according to claim 17, which is obtained by curing without using a catalyst that promotes hydrosilylation. a heating chamber;
19. A water and oil repellent film according to claim 17 or 18 located on a surface of an element which is at least part of said heating chamber and which is exposed to heat. A structure comprising the water- and oil-repellent film according to claim 17 or 18 located on a surface exposed to heat.