JP2016033190A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition that is low cost and has sufficient water repellency and non-adhesiveness, and to provide a roller, a mold, a plate, a chute, a hopper, or a member for the outermost surface of a cooking tool using the coating composition and a roller, a mold, a plate, a chute, a hopper, or a cooking tool.SOLUTION: A coating composition contains a trialkoxysilane compound, an inorganic filler, a catalyst, a siloxane oligomer having a molecular weight of 12,000 or less and having a specific structure, water, and an organic solvent. A coating composition may be obtained by mixing a material A containing the inorganic filler, water, and the organic solvent with a material B containing the trialkoxysilane compound, the catalyst, the siloxane oligomer, and the organic solvent.SELECTED DRAWING: None

Description

  The present invention relates to a coating composition. The present invention also relates to a roller, a mold, a plate, a chute, a hopper, or a cooking utensil, and a roller, a mold, a plate, a chute, a hopper, or a cooking utensil using the coating composition. Related.

  In recent years, when manufacturing adhesive tapes, sanitary materials (paper diapers, sanitary products, etc.), rubber tires, etc., cost reduction and quality improvement have been demanded. The rollers and molds used in these processes use acrylic adhesives for adhesive tapes, hot melt adhesives for non-woven fabrics and polymer absorbers for hygiene materials, and rubber tires before vulcanization for rubber tires. In order to impart non-adhesiveness to raw rubber, silicone resin coating using a silicone resin such as polydimethylsiloxane is performed.

  Moreover, when cooking with a gas cooking appliance, the antifouling property, non-adhesiveness, and durability improvement with respect to foodstuff are calculated | required. In general, a grill net, a grill plate, or the like used in these gas cooking utensils is coated with a fluororesin in order to impart antifouling properties.

  However, the heat resistance of the fluororesin is about 260 ° C. when polytetrafluoroethylene (PTFE) is taken as an example, and the heat resistance of other fluororesins is not sufficient. In addition, the fluororesin itself is soft and wear resistance is insufficient. For this reason, the ceramic coating which has a siloxane bond (Si-O-Si) is employ | adopted also in the gas cooking appliance.

  However, none of these coatings provides a coating having sufficient water repellency and non-tackiness.

  On the other hand, a paint for obtaining an organic-inorganic hybrid coating having a three-dimensional crosslinked matrix structure having a siloxane bond using alkyltrialkoxysilane as a starting material is also commercially available. Patent document 1 etc. are known as an invention example which improved the non-adhesiveness of this kind of coating material.

Patent No. 5017457

  In the non-adhesive coating composition of Patent Document 1, the corrosion resistance, water resistance, etc. have been improved by including hexagonal boron nitride in addition to alkoxysilane (alkyltrialkoxysilane such as methyltrimethoxysilane). Is the main feature. However, non-adhesive coating compositions containing such alkoxysilanes (such as alkyltrialkoxysilanes such as methyltrimethoxysilane) have a coating with a three-dimensional structure matrix structure having siloxane bonds. Since there are few organic components, such as an alkyl group, water repellency and non-adhesiveness are inadequate, and even if hexagonal boron nitride is added, it cannot be said that it is enough. Further, since hexagonal boron nitride is a plate-like crystal, it is difficult to uniformly disperse it in the paint, and since it is an expensive material, it has a demerit that the cost of the paint is increased.

  For these reasons, an object of the present invention is to provide a coating composition that is inexpensive and has sufficient water repellency and non-tackiness. Another object is to provide a roller, a mold, a plate, a chute, a hopper, or a cooking utensil, and a roller, a mold, a plate, a chute, a hopper, or a cooking utensil using the coating composition. And

  As a result of intensive studies, the present inventors have found that in a coating composition for forming a coating film containing an organic-inorganic hybrid substance having a three-dimensional cross-linked matrix structure having a siloxane bond using a trialkoxysilane compound as a starting material. A siloxane oligomer having a specific structure (a siloxane oligomer (1) having an alkylalkoxysiloxane structure, both ends having an alkyldialkoxysilyl group and a molecular weight of 12,000 or less, and / or a dialkylsiloxane structure) It was found that the water repellency and non-tackiness of the coating film are improved by adding a siloxane oligomer (2)) having a terminal end of a trialkylsilyl group and a trialkoxysilyl group and a molecular weight of 12,000 or less. In addition, since the siloxane oligomer used in this case is a relatively inexpensive material and only a small amount needs to be added to the starting material, a coating composition can be obtained at a low cost. Since such a coating composition is excellent in water repellency and non-adhesiveness, it can be used for a wide variety of applications such as rollers, molds, plates, chutes, hoppers, and cooking utensils.

  The present invention has been completed by further research based on such knowledge. That is, the present invention includes the following configurations.

Item 1. A coating composition containing a trialkoxysilane compound, an inorganic filler, a catalyst, a siloxane oligomer, water, and an organic solvent,
The siloxane oligomer has an alkylalkoxysiloxane structure, both ends are alkyl dialkoxysilyl groups, a siloxane oligomer (1) having a molecular weight of 12000 or less, and / or a dialkylsiloxane structure, and a terminal is a trialkyl. A coating composition containing a siloxane oligomer (2) which is a silyl group and a trialkoxysilyl group and has a molecular weight of 12,000 or less.

  Item 2. The trialkoxysilane compound content in the coating composition is 15 to 50% by weight, the inorganic filler content is 5 to 40% by weight, the catalyst content is 0.02 to 5% by weight, the water The content of the organic solvent is 5 to 50% by weight, and the content of the siloxane oligomer is 0.1 to 20 parts by weight with respect to 100 parts by weight of the trialkoxysilane compound. Item 2. The coating composition according to Item 1.

  Item 3. Item 3. The coating composition according to Item 1 or 2, further comprising an inorganic pigment.

  Item 4. Item 4. The coating composition according to Item 3, wherein the content of the inorganic pigment is 5 to 40% by weight.

Item 5. A coating composition comprising a mixture of A material and B material,
The A material includes an inorganic filler, water, and an organic solvent,
The B material includes a trialkoxysilane compound, a catalyst, a siloxane oligomer, and an organic solvent,
The siloxane oligomer has an alkylalkoxysiloxane structure, both ends are alkyl dialkoxysilyl groups, a siloxane oligomer (1) having a molecular weight of 12000 or less, and / or a dialkylsiloxane structure, and a terminal is a trialkyl. The coating composition which is a siloxane oligomer (2) which is a silyl group and a trialkoxysilyl group and has a molecular weight of 12,000 or less.

Item 6. The content of the inorganic filler in the A material is 10 to 50% by weight, the water content is 10 to 50% by weight, and the organic solvent content is 10 to 50% by weight,
The trialkoxysilane compound content in the B material is 80 to 98% by weight, the catalyst content is 0.1 to 10% by weight, the siloxane oligomer content is 0.1 to 20 parts by weight, Item 6. The coating composition according to Item 5, wherein the content of the organic solvent is 1 to 10% by weight.

  Item 7. Item 7. The coating composition according to Item 5 or 6, wherein the A material further contains an inorganic pigment.

  Item 8. Item 8. The coating composition according to Item 7, wherein the content of the inorganic pigment in the A material is 10 to 50% by weight.

  Item 9. Item 9. The coating composition according to any one of Items 5 to 8, wherein the content of the A material in the coating composition is 50 to 90% by weight and the content of the B material is 10 to 50% by weight.

  Item 10. Item 10. The coating composition according to any one of Items 1 to 9, wherein the trialkoxysilane compound is at least one selected from the group consisting of alkyltrialkoxysilane, alkenyltrialkoxysilane, and aryltrialkoxysilane.

  Item 11. The trialkoxysilane compound has the general formula (3):

[Wherein R ⁹ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a monocyclic or bicyclic aryl group; R ¹⁰ is the same or different and each represents an alkyl having 1 to 6 carbon atoms. Or a monocyclic or bicyclic aryl group. ]
Item 11. The coating composition according to any one of Items 1 to 10, which is a compound represented by:

  Item 12. The trialkoxysilane compound includes methyltrimethoxysilane, methyltriethoxysilane, methyltri (n-propoxy) silane, methyltri (i-propoxy) silane, methyltri (n-butoxy) silane, methyl (n-pentoxy) silane, methyl (N-hexoxy) silane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri (n-propoxy) silane, ethyltri (i-propoxy) silane, ethyltri (n-butoxy) silane, ethyltri (n- Pentoxy) silane, ethyl (n-hexoxy) silane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (n-propoxy) silane, n-propyltrimethoxysilane, n-pro Lutriethoxysilane, n-propyltri (n-propoxy) silane, n-propyltri (i-propoxy) silane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri (n-propoxy) silane , I-propyltri (i-propoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, allyltri (n-propoxy) silane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri (n- Propoxy) silane, n-butyltri (i-propoxy) silane, n-butyltri (n-butoxy) silane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-pentyltriethoxysilane, n- Pentilly (i-propoxy) sila N-pentyltri (n-butoxy) silane, n-pentyltri (n-pentoxy) silane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyl (n-propoxy) silane, cyclopentyl (i-propoxy) silane, cyclopentyltri ( n-butoxy) silane, cyclopentyltri (n-pentoxy) silane, cyclopentyltricyclopentoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltri (n-propoxy) silane, n-hexyltri ( i-propoxy) silane, n-hexyltri (n-butoxy) silane, n-hexyltri (n-pentoxy) silane, n-hexyltri (n-hexoxy) silane, cyclohexyltrimethoxysilane, Cyclohexyltriethoxysilane, Cyclohexyltri (n-propoxy) silane, Cyclohexyltri (n-butoxy) silane, Cyclohexyltri (n-pentoxy) silane, Cyclohexyltri (n-hexoxy) silane, Cyclohexyltricyclohexoxysilane, Phenyltrimethoxy Silane, phenyltriethoxysilane, phenyltri (n-propoxy) silane, phenyltri (n-butoxy) silane, phenyltri (n-pentoxy) silane, phenyltri (n-hexoxy) silane, phenyltri (n-hexoxy) Item 12. The coating composition according to any one of Items 1 to 11, which is at least one selected from the group consisting of silane and phenyltri (phenoxy) silane.

  Item 13. Item 13. The coating composition according to any one of Items 1 to 12, wherein the inorganic filler is at least one selected from the group consisting of silica, alumina, titania, zirconia, zinc oxide, silicon carbide, silicon nitride, iron oxide, and mica. object.

  Item 14. Item 14. The coating composition according to any one of Items 1 to 13, wherein the catalyst is at least one selected from the group consisting of formic acid, acetic acid, propionic acid, acrylic acid, hydrochloric acid, sulfuric acid, and nitric acid.

  Item 15. Item 15. The coating composition according to any one of Items 1 to 14, wherein the siloxane oligomer (1) further has an alkyl-substituted alkoxysiloxane structure and / or a dialkylsiloxane structure.

  Item 16. The siloxane oligomer (1) has the general formula (1):

[Wherein R ^{1 to} R ⁵ are the same or different and each represents an alkyl group; X is a linear, branched or cyclic silicon-containing group; a is an integer of 1 to 130; b is an integer of 0 to 65; c Is an integer from 0 to 155. ]
Is a compound having a molecular weight of 12000 or less,
The siloxane oligomer (2) has the general formula (2):

[Wherein, R ^{6 to} R ⁸ are the same or different and each represents an alkyl group; d is an integer of 1 to 155. ]
Item 16. The coating composition according to any one of Items 1 to 15, which is a compound represented by:

  Item 17. Item 17. The coating composition according to any one of Items 1 to 16, wherein the organic solvent is an alcohol.

  Item 18. Item 18. The coating composition according to item 17, wherein the alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 2-methyl-2-propanol. object.

Item 19. The inorganic pigment includes Cr ₂ O ₃ , Fe ₂ O ₃ , TiO ₂ , CuCr ₂ O ₄ , Cu (Cr, Mn) ₂ O ₄ , Cu (Fe, Mn) ₂ O ₄ , Co (Fe, Cr) _2. Item 19. The coating composition according to any one of Items 3 to 18, which is at least one selected from the group consisting of O ₄ , CoAl ₂ O ₄ , Co ₂ TiO ₄ , and silica black.

  Item 20. Item 20. The coating composition according to any one of Items 1 to 19, which is a composition for the outermost surface of a roller, mold, plate, chute, hopper, or cooking utensil.

  Item 21. Item 21. A coating film using the coating composition according to any one of items 1 to 20.

  Item 22. Item 22. The coating film according to Item 21, wherein the thickness is 5 μm or more.

  Item 23. Item 22. The coating film according to Item 21 or 22, which is a coating film for an outermost surface of a roller, a mold, a plate, a chute, a hopper, or a cooking utensil.

  Item 24. Item 24. A member for an outermost surface of a roller, a mold, a plate, a chute, a hopper, or a cooking utensil, comprising the coating film according to any one of Items 21 to 23.

  Item 25. Item 25. A roller, a mold, a plate, a chute, a hopper, or a cooking utensil comprising the outermost surface member of the roller, mold, plate, chute, hopper, or cooking utensil according to Item 24.

  According to the present invention, a coating composition that is inexpensive and has sufficient water repellency and non-adhesiveness can be provided. Moreover, the roller, metal mold | die, plate, chute | shoot, hopper, or the member for outermost surfaces of a cooking utensil using the said coating composition, and a roller, a metal mold | die, a plate, a chute | shoot, a hopper, or a cooking utensil can also be provided. . In addition, if the coating composition of the present invention is used, the water repellency and non-adhesiveness of the outermost surface coating such as a roller, a mold, a plate, a chute, a hopper, and a cooking utensil are not impaired and can be used for a long period of time. It can be used, and can improve the quality of products such as paper, non-woven fabric, film, sheet, resin, mold-molded product, food, and the like, and can improve the yield and careability of the product.

1. Coating composition The coating composition of the present invention comprises a trialkoxysilane compound, an inorganic filler, a catalyst, a siloxane oligomer, water, and an organic solvent.

  By using a trifunctional trialkoxysilane compound, the crosslinking density of the silica matrix is reduced, and a coating film excellent in film formability and flexibility can be obtained.

  Examples of such trifunctional trialkoxysilane compounds include alkyltrialkoxysilanes, alkenyltrialkoxysilanes, aryltrialkoxysilanes, and the like. Among these, general formula (3):

[Wherein R ⁹ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a monocyclic or bicyclic aryl group; R ¹⁰ is the same or different and each represents an alkyl having 1 to 6 carbon atoms. Or a monocyclic or bicyclic aryl group. ]
The compound shown by these is mentioned.

In General Formula (3), R ⁹ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a monocyclic or bicyclic aryl group.

As the alkyl group represented by R ⁹ , the larger the carbon number, the better the hydrophobicity, but any of 1, 2, 3, 4, 5, 6 can be used. As the alkyl group represented by R ⁹ , any of a chain alkyl group, a branched alkyl group and a cyclic alkyl group can be employed, and a chain alkyl group and a cyclic alkyl group are preferred. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group.

As the alkenyl group represented by R ⁹ , a larger carbon number tends to be more hydrophobic, but any of 2, 3, 4, 5, and 6 carbon atoms can be used. In addition, as the alkenyl group represented by R ⁹ , both a chain alkenyl group and a branched alkenyl group can be adopted, and a chain alkenyl group is preferable. Specifically, a vinyl group, an allyl group, etc. are illustrated.

As the aryl group represented by R ⁹ , both monocyclic and bicyclic rings can be used, and a phenyl group, a naphthyl group, and the like, particularly a phenyl group are preferably exemplified.

In the general formula (3), R ¹⁰ is the same or different and each represents an alkyl group having 1 to 6 carbon atoms, or a monocyclic or bicyclic aryl group.

The alkyl group represented by R ¹⁰ is preferably an alkyl group having 1 to 4 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms because the hydrolysis rate becomes slow when the carbon number is large. As the alkyl group represented by R ¹⁰ , any of a chain alkyl group, a branched alkyl group, and a cyclic alkyl group can be employed, but a chain alkyl group and a branched alkyl group are preferable. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group.

As the aryl group represented by R ¹⁰ , both monocyclic and bicyclic rings can be used, and a phenyl group, a naphthyl group, and the like, particularly a phenyl group are preferably exemplified.

These R ¹⁰ may be the same or different.

  Specific examples of such trifunctional trialkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltri (n-propoxy) silane, methyltri (i-propoxy) silane, and methyltri (n- Butoxy) silane, methyl (n-pentoxy) silane, methyl (n-hexoxy) silane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri (n-propoxy) silane, ethyltri (i-propoxy) silane , Ethyltri (n-butoxy) silane, ethyltri (n-pentoxy) silane, ethyl (n-hexoxy) silane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (n-propoxy) silane, n- Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri (n-propoxy) silane, n-propyltri (i-propoxy) silane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i -Propyltri (n-propoxy) silane, i-propyltri (i-propoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, allyltri (n-propoxy) silane, n-butyltrimethoxysilane, n-butyltri Ethoxysilane, n-butyltri (n-propoxy) silane, n-butyltri (i-propoxy) silane, n-butyltri (n-butoxy) silane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-pentyltri (N-propoxy) silane, n Pentyltri (i-propoxy) silane, n-pentyltri (n-butoxy) silane, n-pentyltri (n-pentoxy) silane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyl (n-propoxy) silane, cyclopentyl (i- Propoxy) silane, cyclopentyltri (n-butoxy) silane, cyclopentyltri (n-pentoxy) silane, cyclopentyltricyclopentoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltri (n-propoxy) ) Silane, n-hexyltri (i-propoxy) silane, n-hexyltri (n-butoxy) silane, n-hexyltri (n-pentoxy) silane, n-hexyltri (n-hexoxy) silane Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltri (n-propoxy) silane, cyclohexyltri (n-butoxy) silane, cyclohexyltri (n-pentoxy) silane, cyclohexyltri (n-hexoxy) silane, cyclohexyltricyclohexyl Toxisilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri (n-propoxy) silane, phenyltri (n-butoxy) silane, phenyltri (n-pentoxy) silane, phenyltri (n-hexoxy) silane, phenyl And triphenoxysilane. These trialkoxysilane compounds may be used alone or as a raw material in combination of two or more. Among these, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri (n-propoxy) silane, One or more of phenyltrimethoxysilane, phenyltriethoxysilane, etc., especially methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, etc. It is particularly preferable to use one or more of these as starting materials because the coating film is flexible and can improve non-adhesiveness.

  In addition, when a tetrafunctional tetraalkoxysilane is used alone instead of a trifunctional trialkoxysilane compound as a starting material, a silica film is obtained. However, since it becomes a hard and brittle coating film, it is 1 μm or more. Cracks and the like occur when the film is thick. Moreover, since there is no organic component, non-adhesiveness is insufficient. However, as long as the effects of the present invention are not impaired, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane may be included in the coating composition of the present invention. Specifically, when a small amount of 10 parts by weight or less (particularly 0.1 to 10 parts by weight) of tetraalkoxysilane is added to 100 parts by weight of the trialkoxysilane compound, the siloxane crosslinking density increases. Further, a trialkoxysilane compound containing tetraalkoxysilane as an impurity may be used.

  Using such a trifunctional trialkoxysilane compound as a starting material, a general formula (4):

[Wherein R ⁹ is the same as defined above. ]
An organic-inorganic hybrid material having a three-dimensional crosslinked matrix structure having a siloxane bond having a structure represented by In the general formula (4), R ⁹ is the same as described above. That is, the organic-inorganic hybrid material formed using the coating composition of the present invention is different from a silicone resin such as polydimethylsiloxane.

  In the coating composition of the present invention, the content of the trialkoxysilane compound is preferably 15 to 50% by weight, and more preferably 20 to 45% by weight. By setting the content of the trialkoxysilane compound within this range, a more uniform organic-inorganic hybrid coating film can be formed.

  The organic-inorganic hybrid material as described above can be obtained by hydrolysis using the above trifunctional trialkoxysilane compound as a starting material in combination with a catalyst (acid, base, etc.). By hydrolyzing using a catalyst in combination, the hydrolysis rate can be adjusted more appropriately. Therefore, the hardness of the resulting coating film can be adjusted more appropriately to make a more flexible film.

  Specific examples of such a catalyst include one or more acids such as formic acid, acetic acid, propionic acid, acrylic acid, hydrochloric acid, sulfuric acid, and nitric acid, particularly 1 such as formic acid, acetic acid, propionic acid, acrylic acid, and hydrochloric acid. Although the acid of a seed | species or more is used suitably, it is not limited to these.

  The hydrolysis may be carried out using a base such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, calcium hydroxide or guanidine as a catalyst. However, it is preferable to use an acid as the catalyst because the hydrolysis rate is slower and the resulting coating film becomes more flexible.

  In the coating composition of the present invention, the content of the catalyst is preferably 0.02 to 5% by weight, and more preferably 0.05 to 3% by weight. By setting the content of the catalyst within this range, the alkoxy group of the trialkoxysilane compound is hydrolyzed to form a silanol group, and the condensation reaction can proceed more smoothly.

  Moreover, 0.01-5 weight part is preferable with respect to 100 weight part of said trialkoxysilane compounds, and, as for content of the said catalyst, 0.1-3 weight part is more preferable. By setting the content of the catalyst within this range, the alkoxy group of the trialkoxysilane compound is hydrolyzed to a silanol group, and the condensation reaction can proceed more smoothly.

  Moreover, as a solvent of the coating composition of this invention, it is preferable to use both water and an organic solvent, and water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2- Alcohols such as methyl-2-propanol; propylene glycol derivatives such as propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; 1-methyl-2-pyrrolidone; N , N-dimethylformamide and the like. As an organic solvent, you may use individually by 1 type and may use 2 or more types together. In particular, the organic solvent preferably contains an alcohol.

  In the coating composition of the present invention, the content of water as a solvent is preferably 5 to 50% by weight, more preferably 10 to 45% by weight. By setting the water content within this range, the inorganic filler can be more uniformly dispersed and the trialkoxysilane compound can be hydrolyzed more appropriately.

  In the coating composition of the present invention, the content of the organic solvent as the solvent is preferably 5 to 50% by weight, more preferably 10 to 45% by weight. By setting the content of the organic solvent within this range, the stability of the coating composition is further improved.

  The coating composition of the present invention contains an inorganic filler in addition to the above components. As the inorganic filler, inorganic particles are preferable from the viewpoint of facilitating uniform dispersion in the coating composition.

  1-1000 nm is preferable and, as for the average primary particle diameter of an inorganic filler, 5-500 nm is more preferable. By setting it within this range, aggregation of inorganic fillers is further suppressed, and uniform mixing (dispersion) with trialkoxysilane compounds is more possible, and the coating film surface is made smoother, and inorganic fillers fall off more. Can be difficult. In addition, the average particle diameter of an inorganic filler shall be measured by electron microscope (SEM) observation.

  The inorganic filler is not particularly limited, and examples thereof include silica, alumina, titania, zirconia, zinc oxide, silicon carbide, silicon nitride, iron oxide, mica and the like. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

  In the coating composition of the present invention, the content of the inorganic filler is preferably 5 to 40% by weight, and more preferably 10 to 35% by weight. By setting the content of the inorganic filler within this range, when the trialkoxysilane compound undergoes dehydration condensation, it is possible to suppress volume shrinkage of the coating film and prevent cracks and the like from entering the coating film.

  The coating composition of the present invention contains a siloxane oligomer in addition to the above components. The siloxane oligomer used in the present invention has an alkylalkoxysiloxane structure, both ends are alkyldialkoxysilyl groups, a molecular weight of 12000 or less, and / or a dialkylsiloxane structure. It contains a siloxane oligomer (2) having a terminal end of a trialkylsilyl group and a trialkoxysilyl group and a molecular weight of 12,000 or less. Thereby, many alkyl groups (organic components) are distributed on the surface of the coating film prepared using the coating composition of the present invention, and the water repellency and non-adhesiveness can be sufficiently improved.

  The molecular weight of such a siloxane oligomer is not particularly limited, but the molecular weight is preferably 300 to 12,000, more preferably 1,000 to 10,000. By setting the molecular weight within this range, a condensation reaction with the trialkoxylane compound condensation reaction product is performed, and the hardness and strength of the coating film are not further impaired.

  The siloxane oligomer (1) used in the present invention is a compound having an alkylalkoxysiloxane structure and both ends of which are alkyldialkoxysilyl groups, which can further improve the strength of the coating film. When it has a siloxane structure, non-adhesiveness can be further improved. Depending on the synthesis conditions, it may have an alkyl-substituted alkoxysiloxane structure. In the alkyl-substituted alkoxysiloxane structure, the substituent of the alkoxy group is not particularly limited, but for example, an alkyl dialkoxysilyl group such as a methyldimethoxysilyl group is preferable.

  Such a siloxane oligomer (1) is not particularly limited. For example, the general formula (1):

[Wherein R ^{1 to} R ⁵ are the same or different and each represents an alkyl group; X is a linear, branched or cyclic silicon-containing group; a is an integer of 1 to 130; b is an integer of 0 to 65; c Is an integer from 0 to 155. ]
A compound having a molecular weight of 12000 or less is preferred.

In the general formula (1), R ^{1 to} R ⁵ are alkyl groups. The alkyl group represented by R ^{1 to} R ⁵ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, from the viewpoint of non-adhesiveness. Moreover, as an alkyl group shown by R < ¹ > -R < ⁵ >, all of a chain alkyl group, a branched alkyl group, and a cyclic alkyl group can be employ | adopted, and a chain alkyl group and a cyclic alkyl group are preferable. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group, and a methyl group is preferable. . In these R ^{1 to} R ⁵ , R ¹ may be the same or different, R ² may be the same or different, R ³ may be the same or different, and R ⁴ is the same or different. R ⁵ may be the same or different. R ^{1 to} R ⁵ may be the same as or different from each other.

  In the general formula (1), X is a linear, branched or cyclic silicon-containing group, preferably an alkyl dialkoxysilyl group. Specifically, methyldimethoxysilyl group, methyldiethoxysilyl group, methyldi (n-propoxy) silyl group, methyldi (i-propoxy group) silyl group, methyldi (n-butoxy) silyl group, ethyldimethoxysilyl group, ethyl Diethoxysilyl group, ethyldi (n-propoxy) silyl group, ethyldi (i-propoxy) silyl group, ethyldi (n-butoxy) silyl group, n-propoxydimethoxysilyl group, n-propoxydiethoxysilyl group, n-propoxydi (N-propoxy) silyl group, n-propoxydi (i-propoxy group) silyl group, n-propoxydi (n-butoxy) silyl group, i-propoxydimethoxysilyl group, i-propoxydiethoxysilyl group, i-propoxydi ( n-propoxy) silyl group, i-propoxy di (i-propyl) Poxy group) silyl group, i-propoxydi (n-butoxy) silyl group, n-butoxydimethoxysilyl group, n-butoxydiethoxysilyl group, n-butoxydi (n-propoxy) silyl group, n-butoxydi (i-propoxy) Group) silyl group, n-butoxydi (n-butoxy) silyl group and the like are exemplified, and methyldimethoxysilyl group is preferable.

  In the general formula (1), a is preferably an integer of 1 to 130, and more preferably an integer of 2 to 108, from the viewpoint of the hardness and strength of the coating film.

  In the general formula (1), b is preferably an integer of 0 to 65, more preferably an integer of 1 to 54, from the viewpoint of the hardness and strength of the coating film.

  In the general formula (1), c is preferably an integer of 0 to 155, more preferably an integer of 1 to 132, from the viewpoint of non-adhesiveness.

  The siloxane oligomer (1) may be a block oligomer or a random oligomer.

  The siloxane oligomer (2) used in the present invention is not particularly limited. For example, the general formula (2):

[Wherein, R ^{6 to} R ⁸ are the same or different and each represents an alkyl group; d is an integer of 1 to 155. ]
The compound shown by these is preferable.

In General formula (2), R < ⁶ > -R < ⁸ > is an alkyl group, The specific example and preferable example are the same as that of R < ¹ > -R < ⁵ >. That is, the methyl group is most preferable from the viewpoint of non-adhesiveness. As R ^{6 to} R ⁸ , R ⁶ may be the same or different, R ⁷ may be the same or different, and R ⁸ may be the same or different. R ^{6 to} R ⁸ may be the same as or different from each other.

  In the general formula (2), d is preferably an integer of 1 to 155, and more preferably an integer of 2 to 132, from the viewpoint of non-adhesiveness.

  The siloxane oligomer (2) may be a block oligomer or a random oligomer.

  These siloxane oligomers (siloxane oligomer (1) and siloxane oligomer (2)) may be used alone or in combination of two or more. That is, the siloxane oligomer (1) and the siloxane oligomer (2) may be used in combination.

  0.1-20 weight part is preferable with respect to 100 weight part of said trialkoxysilane compounds, and, as for content of a siloxane oligomer, 0.5-15 weight part is more preferable. By setting the content of the siloxane oligomer within this range, the trialkoxysilane compound can be combined with an organic-inorganic hybrid substance that has undergone a condensation reaction, and the coating film hardness, strength, water repellency and non-adhesiveness are further improved. Can be made.

  When the siloxane oligomer (1) and the siloxane oligomer (2) are used in combination as the siloxane oligomer, the content ratio of the siloxane oligomer (1) and the siloxane oligomer (2) is 1: 9 to 9: 1 ( Weight ratio) is preferable, and 2: 8 to 8: 2 (weight ratio) is more preferable.

  In addition to the above components, the coating composition of the present invention preferably contains an inorganic pigment. As the inorganic pigment, inorganic particles are preferable from the viewpoint of facilitating uniform dispersion in the coating composition.

  The average particle diameter of the inorganic pigment is preferably 100 to 2000 nm, and more preferably 300 to 1000 nm. By setting it within this range, aggregation of inorganic pigments is further suppressed, and uniform mixing (dispersion) with trialkoxysilane compounds is possible, and the coating film surface is made smoother and inorganic pigments fall off more. Can be difficult. The average particle diameter of the inorganic pigment is measured by a laser diffraction / scattering method (microtrack method).

The inorganic pigments include, but are not particularly limited, for _{example, Cr 2 O 3, Fe 2} O 3, TiO 2, CuCr 2 O 4, Cu (Cr, Mn) 2 O 4, Cu (Fe, Mn) ₂ O ₄ , Co (Fe, Cr) ₂ O ₄ , CoAl ₂ O ₄ , Co ₂ TiO ₄ , silica black and the like. An inorganic pigment may be used individually by 1 type, and may use 2 or more types together.

  When an inorganic pigment is included in the coating composition of the present invention, the content of the inorganic pigment is preferably 5 to 40% by weight, and more preferably 10 to 35% by weight. By setting the content of the inorganic pigment within this range, the coating film can be uniformly colored without further inhibiting the dehydration condensation reaction of the trialkoxysilane compound.

  In addition to the above components, the coating composition of the present invention includes carbon particles (carbon black, graphite, etc.), flow aid, charging aid, degassing agent, thickener, anti-settling agent, anti-sagging agent, dispersion One or more of an agent, an antifoaming agent, a smoothing agent (leveling agent), an anti-drying agent, a surfactant and the like may be included within a range not impairing the effects of the present invention.

  The form of the coating composition of the present invention is not particularly limited.

  For example, the above components may be mixed simultaneously or sequentially.

  When mixing each said component simultaneously, what is necessary is just to mix so that the said component may become the said content.

  On the other hand, when mixing each said component sequentially, A material containing the said inorganic filler, water, and an organic solvent, B material containing the said trialkoxysilane compound, the said siloxane oligomer, the said catalyst, and the said organic solvent May be mixed to form a liquid composition (liquid paint). When the inorganic pigment is included in the coating composition of the present invention, it is preferably included in the A material. In this case, it is considered that the alkoxy group of the trialkoxysilane compound is not substituted with a hydroxyl group at the time of only the B material before mixing with the A material. By mixing with the A material, the alkoxy group is hydrolyzed to become a hydroxyl group, the polymerization reaction is started, and a Si—O—Si network is formed. In addition, since the siloxane oligomer is contained in the B material, it can be combined with an organic-inorganic hybrid substance obtained by condensation reaction of the trialkoxysilane compound. Thereby, since an alkyl group is exposed on the surface, sufficient water repellency and non-tackiness can be imparted.

  The solvent in the A material and the B material is not particularly limited, but the solvent in the A material is preferably water and the above organic solvent, and the solvent in the B material is preferably the above organic solvent.

  When mixing the above A material and B material and obtaining the coating composition of this invention, 10-50 weight% is preferable and, as for content of the inorganic filler in A material, 20-40 weight% is more. preferable. By setting the content of the inorganic filler within this range, when the trialkoxysilane compound undergoes dehydration condensation, volume shrinkage of the coating film can be further suppressed, and cracks and the like can be prevented from entering the coating film.

  Moreover, 20-100 weight part is preferable with respect to 100 weight part of trialkoxysilane compounds in B material, and, as for content of the inorganic filler in A material, 30-90 weight part is more preferable. By setting the content of the inorganic filler within this range, when the trialkoxysilane compound undergoes dehydration condensation, volume shrinkage of the coating film can be further suppressed, and cracks and the like can be prevented from entering the coating film.

  When mixing the above A material and B material and obtaining the coating composition of this invention, 10-50 weight% is preferable and, as for content of the water in A material, 15-45 weight% is more preferable. . By setting the water content within this range, the inorganic filler can be more uniformly dispersed and the trialkoxysilane compound can be hydrolyzed. Moreover, 5-50 weight% is preferable and, as for content of the organic solvent in A material, 10-45 weight% is more preferable. By making content of an organic solvent into this range, an inorganic filler is disperse | distributed more uniformly and the stability of a coating composition improves more.

  When the A material and the B material as described above are mixed to obtain the coating composition of the present invention, when the inorganic pigment is included in the A material, the content of the inorganic pigment in the A material is 10 to 10. 50 weight% is preferable and 20 to 40 weight% is more preferable. By setting the content of the inorganic pigment within this range, when the trialkoxysilane compound undergoes dehydration condensation, volume shrinkage of the coating film can be further suppressed, and cracks and the like can be prevented from entering the coating film.

  When the inorganic pigment is included, the content of the inorganic pigment in the A material is preferably 20 to 100 parts by weight, preferably 30 to 90 parts by weight with respect to 100 parts by weight of the trialkoxysilane compound in the B material. Is more preferable. By setting the content of the inorganic pigment within this range, when the trialkoxysilane compound undergoes dehydration condensation, volume shrinkage of the coating film can be further suppressed, and cracks and the like can be prevented from entering the coating film.

  When the coating material of the present invention is obtained by mixing the A material and the B material as described above, the trialkoxysilane compound content in the B material is preferably 80 to 98% by weight, and 85 to 95% by weight. Is more preferable. By setting the content of the trialkoxysilane compound within this range, a more uniform organic-inorganic hybrid coating film can be formed.

  When the A material and the B material as described above are mixed to obtain the coating composition of the present invention, the content of the siloxane oligomer in the B material is preferably 0.1 to 20% by weight, and 0.5 to 15 Weight percent is more preferred. By setting the content of the siloxane oligomer within this range, the trialkoxysilane compound can be hydrolyzed to form silanol to be more easily bonded to the organic-inorganic hybrid substance generated when the condensation reaction occurs. Thereby, since an alkyl group becomes easy to be exposed on the surface, more sufficient water repellency and non-adhesiveness can be provided. In addition, the hardness and strength of the organic-inorganic hybrid coating film can be further maintained.

  Moreover, 0.1-20 weight part is preferable with respect to 100 weight part of trialkoxysilane compounds in B material, and, as for content of the siloxane oligomer in B material, 0.5-15 weight part is more preferable. By setting the content of the siloxane oligomer within this range, the trialkoxysilane compound can be hydrolyzed to form silanol to be more easily bonded to the organic-inorganic hybrid substance generated when the condensation reaction occurs. Thereby, since an alkyl group becomes easy to be exposed on the surface, more sufficient water repellency and non-adhesiveness can be provided. In addition, the hardness and strength of the organic-inorganic hybrid coating film can be further maintained.

  When the coating material of the present invention is obtained by mixing the A material and the B material as described above, the content of the catalyst in the B material is preferably 0.1 to 10% by weight, and 0.2 to 5% by weight. % Is more preferable. By setting the content of the catalyst within this range, the alkoxy group of the trialkoxysilane compound can be further hydrolyzed to form a silanol group, and the condensation reaction can proceed more smoothly.

  When mixing the above A material and B material and obtaining the coating composition of this invention, 1-10 weight% is preferable and, as for content of the organic solvent in B material, 2-8 weight% is more. preferable. By setting the content of the organic solvent within this range, the stability of the coating composition is further improved.

  When mixing the A material and the B material as described above to obtain the coating composition of the present invention, the mixing ratio of the A material and the B material is from the viewpoint of obtaining an organic-inorganic hybrid coating film having a more uniform composition. It is preferable to mix so that the content of the A material is 50 to 90% by weight (particularly 60 to 80% by weight) and the content of the B material is 10 to 50% by weight (particularly 20 to 40% by weight).

  Since the coating composition of the present invention described above has sufficiently excellent water repellency and non-adhesiveness, it can be applied to a wide variety of applications, for example, rollers, molds, plates, chutes, hoppers, It can be applied to cooking utensils. In this case, since the coating composition of the present invention has sufficiently excellent water repellency and non-adhesiveness, it is preferably used as the outermost surface composition.

  A roller, a mold, a plate, a chute, a hopper, and a cooking utensil that can use the coating composition of the present invention are not particularly limited.

  As a roller, for example, it can be applied to any of a drying roller, a coating roller, a transfer roller, a bonding roller, a pressure roller, a guide roller, a roller for applying a pattern to a siding material (outer wall material), a papermaking roller, a printing roller, etc. Is possible. Examples of the mold include, for example, a mold for manufacturing sanitary materials, a mold for manufacturing rubber tires, a mold for manufacturing automobile parts, various urethane molds, a mold for forming a hot melt adhesive into a solid, a solid hot melt The present invention can be applied to any mold for extruding an adhesive. As a plate, for example, any of a plate used in a process of bonding a nonwoven fabric and a water-absorbing polymer material, a plate on which resin pellets are slid, and the like can be applied. The chute can be applied to any of a chute for a machine for weighing food, a chute for feeding a resin material into a molding machine, and the like. The hopper can be applied to any of a hopper for a machine for weighing food, a hopper for charging powder, and the like. The cooking utensil can be applied to any of grills, pans, frying pans, grill dishes, and the like.

2. Coating Film The coating film of the present invention is obtained using the coating composition of the present invention.

  When forming the coating film of this invention, it is preferable to apply | coat using an air spray with respect to a target object (a roller, a metal mold | die, a plate, a chute | shoot, a hopper, a cooking utensil etc.).

  After coating, it is preferable to perform drying and baking. As drying conditions, it may be dried at room temperature for about 10 to 120 minutes, or forcibly dried at about 50 to 100 ° C. for about 1 to 60 minutes. Moreover, by baking, alkyl trialkoxysilane can be dehydrated and polymerized to form a more uniform coating film. The firing temperature is preferably about 80 to 280 ° C, more preferably about 100 to 250 ° C. The heating time may be determined according to the size of the substrate and the heat capacity, and is not particularly limited, but is usually preferably about 10 to 120 minutes. Thereby, the coating film of the present invention is obtained.

  The thickness of this coating film is preferably 5 μm or more, and more preferably 10 μm or more. The durability can be further improved by setting the thickness of the coating film to 5 μm or more. Further, the upper limit value of the thickness of the coating film is not particularly limited, but is usually about 60 μm. Conventionally, when the coating film is thick, defects such as cracks have occurred. However, in the coating film using the coating composition of the present invention, defects such as cracks are hardly generated even when the coating film is thick.

3. Surface member for roller, mold, plate, chute, hopper, cooking utensil, etc. The roller, die, plate, chute, hopper, and member for top surface of cooking utensil of the present invention are the paints of the present invention described above. It consists of a coating film using the composition and is formed on the outermost surface of rollers, molds, plates, chutes, hoppers, and cooking utensils. More specifically, when the coating composition of the present invention is a liquid paint, the coating composition is preferably composed of a coating film applied using air spray. The method for forming the coating film is as described above.

4). Roller, mold, plate, chute, hopper, and cooking utensil The roller, mold, plate, chute, hopper, and cooking utensil of the present invention are the above-described roller, mold, plate, chute, hopper, And a member for the outermost surface of the cooking utensil. Specifically, the roller, mold, plate, chute, hopper, and cooking utensil of the present invention are the coating film of the present invention for the roller, mold, plate, chute, hopper, and utensil of the present invention on the substrate. It is preferable to provide. In order to improve the wear resistance of the coating film, a sprayed layer may be introduced between the substrate and the coating film of the present invention.

  The material for the substrate is not particularly limited. For example, metals such as general steel, special steel, stainless steel, aluminum and aluminum alloy; resins such as plastic; nonmetals such as carbon materials and ceramics; fiber reinforced plastic (FRP), carbon fiber reinforced plastic (CFRP) Any of these composite materials can be used.

  The shape of the substrate is not particularly limited, and the roller is preferably a cylindrical shape, but may not be a cylindrical shape.

  In order to increase the adhesion between the base material and the roller, mold, plate, chute, hopper, and outermost member of the cooking utensil of the present invention, the surface of the base material should be rough (roughen the surface). Is preferred. As a method of making the surface of the substrate uneven, there are etching treatment in an acid or alkaline aqueous solution, application of a rough surface forming agent, metal or ceramic spraying, shot blasting, etc., among them metal, ceramics, cermet spraying Is preferable because the coating layer can be firmly held at the same time the surface is made uneven.

  In the roller, mold, plate, chute, hopper, and cooking utensil of the present invention, in order to improve the adhesion between the substrate and the coating layer (the coating film of the present invention), the substrate and the roller of the present invention, the mold A primer layer may be provided between the plate, the chute, the hopper, and the outermost member of the cooking utensil. As the primer layer, a layer using a commercially available product for coating a silicone resin can be used. Examples of the main component of the primer layer include vinyltrimethoxysilane and aminopropyltrimethoxysilane.

  The thickness of the primer layer is preferably from 1 to 20 μm, more preferably from 5 to 15 μm, from the viewpoint of uniformly coating the surface of the uneven substrate and improving the adhesion with the outermost coating layer (coating film). preferable.

  Thereafter, the outermost surface is formed using the coating composition of the present invention. When the coating composition of the present invention is a liquid paint, it is preferably applied using an air spray. At this time, as described above, it is preferable to adjust the thickness of the outermost surface layer to be 5 μm or more.

  After coating, it is preferable to perform drying and baking. As drying conditions, it may be dried at room temperature for about 10 to 120 minutes, or forcibly dried at about 50 to 100 ° C. for about 1 to 60 minutes. Also, by firing, the alkyltrialkoxysilane can be dehydrated and condensed to form a more uniform coating film. The firing temperature is preferably about 80 to 280 ° C, more preferably about 100 to 250 ° C. The heating time may be determined according to the size of the substrate and the heat capacity, and is not particularly limited, but is usually preferably about 10 to 120 minutes.

  The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

  The following were used as the siloxane oligomer used in the following Examples and Comparative Examples.

  Moreover, evaluation of each Example and the comparative example was performed as follows.

[Contact angle of water (water repellency)]
A flat test piece was fixed to a CA-A type contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd., and the contact angle of water was measured.

[Pencil hardness (strength)]
In accordance with JIS K5600-5-4, a flat plate test piece is fixed to a HEIDON TYPE 38 device manufactured by Shinto Kagaku Co., Ltd.
Load: 750g
Sweep speed: 1 mm / sec
Sweep distance: 20 mm
The pencil hardness was measured.

[Adhesive tape load measurement (non-adhesive)]
A flat test piece is fixed to a HEIDON TYPE 38 device manufactured by Shinto Kagaku Co., Ltd.
Nichiban Co., Ltd. Cellotape (registered trademark) Part No. CT405AP-18
Width: 18 mm
180 ° peeling method: Evaluation test according to JIS Z0237 standard Measurement conditions: peeling speed 300 mm / min, sweep distance 80 mm
Then, the adhesive tape peeling load measurement was performed.

[Burning test (non-stickiness)]
1 cc of contaminated juice in which soy sauce, sugar and eggs were mixed at a weight ratio of 1: 1: 1 to a flat test piece was dropped with a dropper into an electric furnace and heated at 200 ° C. for 60 minutes. After natural cooling to room temperature, the ease of removal of carbides generated by the contaminated juice was evaluated as follows.
A: The carbide can be easily removed with a finger, and no scorch marks remain on the coating surface.
○: The carbide can be easily removed with a finger, but a burnt mark remains on the coating surface.
About each sample, when it became (circle), the test was stopped and the frequency | count of (double-circle) was evaluated.

Example 1
200 g of water, 170 g of 2-propanol, black pigment Cu (Cr, Mn) ₂ O ₄ (manufactured by Toago Material Technology Co., Ltd., 42-302A, average particle size 800 nm), and silica powder in a 2 liter polypropylene container 175 g (manufactured by Nippon Aerosil Co., Ltd., AEROSIL 50, average primary particle size 30 nm) was added. 600 g of propeller stirring (3 hours) and ultrasonic homogenizer stirring (30 minutes) were performed to prepare 700 g of A material.

  Next, 277.2 g of methyltrimethoxysilane, 2.8 g of siloxane oligomer, 15 g of methanol, and 5 g of acetic acid were added to a 1 liter polypropylene container. Stirring was carried out at 600 rpm propeller (1 hour) to prepare 300 g of B material.

  The above B material was added to the A material container and mixed, and the whole 2 liter polypropylene container was stirred at 200 rpm at 25 ° C. for 12 hours to prepare 1000 g of a coating composition.

  A flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) was subjected to solvent degreasing treatment with methyl ethyl ketone as a base material, and then shot blasting using # 80 alumina particles.

  A coating layer (coating film) was applied by air spray using the coating composition described above on this substrate. After coating, drying was performed at 80 ° C. for 30 minutes. Thereafter, baking was further performed at 250 ° C. for 20 minutes. When the film thickness was measured, it was 30 μm.

  Using this flat plate test piece, the water contact angle measurement, pencil hardness measurement, adhesive tape load test, and scoring test were performed. The results are shown in Table 1.

Example 2
In Example 1, 1000 g of the coating composition was prepared in the same manner except that 271.6 g of methyltrimethoxysilane as material B was not 277.2 g and the amount of siloxane oligomer α was 8.4 g instead of 2.8 g. Prepared.

  A flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) was subjected to solvent degreasing treatment with methyl ethyl ketone as a base material, and then shot blasting using # 80 alumina particles.

  A coating layer (coating film) was applied by air spray using the coating composition described above on this substrate. After coating, drying was performed at 80 ° C. for 30 minutes. Thereafter, baking was further performed at 250 ° C. for 20 minutes. When the film thickness was measured, it was 30 μm.

  Using this flat plate test piece, the water contact angle measurement, pencil hardness measurement, adhesive tape load test, and scoring test were performed. The results are shown in Table 1.

Example 3
In Example 1, 1000 g of the coating composition was carried out in the same manner except that the amount of methyltrimethoxysilane of material B was 263.2 g instead of 277.2 g, and the amount of siloxane oligomer α was 16.8 g instead of 2.8 g. Was prepared.

  A flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) was subjected to solvent degreasing treatment with methyl ethyl ketone as a base material, and then shot blasting using # 80 alumina particles.

  A coating layer (coating film) was applied by air spray using the coating composition described above on this substrate. After coating, drying was performed at 80 ° C. for 30 minutes. Thereafter, baking was further performed at 250 ° C. for 20 minutes. When the film thickness was measured, it was 30 μm.

  Using this flat plate test piece, the water contact angle measurement, pencil hardness measurement, adhesive tape load test, and scoring test were performed. The results are shown in Table 1.

Example 4
In Example 1, 1000 g of a coating composition was prepared in the same manner except that siloxane oligomer β was used instead of siloxane oligomer α added to the B material.

  A flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) was subjected to solvent degreasing treatment with methyl ethyl ketone as a base material, and then shot blasting using # 80 alumina particles.

  A coating layer (coating film) was applied by air spray using the coating composition described above on this substrate. After coating, drying was performed at 80 ° C. for 30 minutes. Thereafter, baking was further performed at 250 ° C. for 20 minutes. When the film thickness was measured, it was 30 μm.

  Using this flat plate test piece, the water contact angle measurement, pencil hardness measurement, adhesive tape load test, and scoring test were performed. The results are shown in Table 1.

Example 5
In Example 4, 1000 g of a coating composition was prepared in the same manner except that 271.6 g of methyltrimethoxysilane as material B was not 277.2 g and the amount of siloxane oligomer β was 8.4 g instead of 2.8 g. Prepared.

  A flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) was subjected to solvent degreasing treatment with methyl ethyl ketone as a base material, and then shot blasting using # 80 alumina particles.

  A coating layer (coating film) was applied by air spray using the coating composition described above on this substrate. After coating, drying was performed at 80 ° C. for 30 minutes. Thereafter, baking was further performed at 250 ° C. for 20 minutes. When the film thickness was measured, it was 30 μm.

  Using this flat plate test piece, the water contact angle measurement, pencil hardness measurement, adhesive tape load test, and scoring test were performed. The results are shown in Table 1.

Example 6
In the same manner as in Example 4, except that 273.2 g of methyltrimethoxysilane as material B was changed to 263.2 g and the amount of siloxane oligomer β was changed to 16.8 g instead of 2.8 g, Prepared.

  A flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) was subjected to solvent degreasing treatment with methyl ethyl ketone as a base material, and then shot blasting using # 80 alumina particles.

  A coating layer (coating film) was applied by air spray using the coating composition described above on this substrate. After coating, drying was performed at 80 ° C. for 30 minutes. Thereafter, baking was further performed at 250 ° C. for 20 minutes. When the film thickness was measured, it was 30 μm.

  Using this flat plate test piece, the water contact angle measurement, pencil hardness measurement, adhesive tape load test, and scoring test were performed. The results are shown in Table 1.

Example 7
In Example 1, 252 g instead of 277.2 g of methyltrimethoxysilane of B material was changed to 8.4 g instead of 2.8 g of siloxane oligomer α, and further siloxane oligomer γ was added to 19.6 g B material. A coating composition of 1000 g was prepared in the same manner as described above.

  A flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) was subjected to solvent degreasing treatment with methyl ethyl ketone as a base material, and then shot blasting using # 80 alumina particles.

  A coating layer (coating film) was applied by air spray using the coating composition described above on this substrate. After coating, drying was performed at 80 ° C. for 30 minutes. Thereafter, baking was further performed at 250 ° C. for 20 minutes. When the film thickness was measured, it was 30 μm.

  Using this flat plate test piece, the water contact angle measurement, pencil hardness measurement, adhesive tape load test, and scoring test were performed. The results are shown in Table 1.

Example 8
In Example 7, 1000 g of a coating composition was prepared in the same manner except that siloxane oligomer β was used instead of siloxane oligomer α.

  A flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) was subjected to solvent degreasing treatment with methyl ethyl ketone as a base material, and then shot blasting using # 80 alumina particles.

  A coating layer (coating film) was applied by air spray using the coating composition described above on this substrate. After coating, drying was performed at 80 ° C. for 30 minutes. Thereafter, baking was further performed at 250 ° C. for 20 minutes. When the film thickness was measured, it was 30 μm.

  Using this flat plate test piece, the water contact angle measurement, pencil hardness measurement, adhesive tape load test, and scoring test were performed. The results are shown in Table 1.

Comparative Example 1
In Example 1, 1000 g of a coating composition was prepared in the same manner except that the siloxane oligomer α was not added to the B material and the amount of methyltrimethoxysilane was 280 g.

  A flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) was subjected to solvent degreasing treatment with methyl ethyl ketone as a base material, and then shot blasting using # 80 alumina particles.

  A coating layer (coating film) was applied by air spray using the coating composition described above on this substrate. After coating, drying was performed at 80 ° C. for 30 minutes. Thereafter, baking was further performed at 250 ° C. for 20 minutes. When the film thickness was measured, it was 30 μm.

  Using this flat plate test piece, the water contact angle measurement, pencil hardness measurement, adhesive tape load test, and scoring test were performed. The results are shown in Table 1.

Claims (25)

A coating composition containing a trialkoxysilane compound, an inorganic filler, a catalyst, a siloxane oligomer, water, and an organic solvent,
The siloxane oligomer has an alkylalkoxysiloxane structure, both ends are alkyl dialkoxysilyl groups, a siloxane oligomer (1) having a molecular weight of 12000 or less, and / or a dialkylsiloxane structure, and a terminal is a trialkyl. A coating composition containing a siloxane oligomer (2) which is a silyl group and a trialkoxysilyl group and has a molecular weight of 12,000 or less. The trialkoxysilane compound content in the coating composition is 15 to 50% by weight, the inorganic filler content is 5 to 40% by weight, the catalyst content is 0.02 to 5% by weight, the water The content of the organic solvent is 5 to 50% by weight, and the content of the siloxane oligomer is 0.1 to 20 parts by weight with respect to 100 parts by weight of the trialkoxysilane compound. The coating composition according to claim 1, wherein Furthermore, the coating composition of Claim 1 or 2 containing an inorganic pigment. The coating composition of Claim 3 whose content of the said inorganic pigment is 5 to 40 weight%. A coating composition comprising a mixture of A material and B material,
The A material includes an inorganic filler, water, and an organic solvent,
The B material includes a trialkoxysilane compound, a catalyst, a siloxane oligomer, and an organic solvent,
The siloxane oligomer has an alkylalkoxysiloxane structure, both ends are alkyl dialkoxysilyl groups, a siloxane oligomer (1) having a molecular weight of 12000 or less, and / or a dialkylsiloxane structure, and a terminal is a trialkyl. The coating composition which is a siloxane oligomer (2) which is a silyl group and a trialkoxysilyl group and has a molecular weight of 12,000 or less. The content of the inorganic filler in the A material is 10 to 50% by weight, the water content is 10 to 50% by weight, and the organic solvent content is 10 to 50% by weight,
The trialkoxysilane compound content in the B material is 80 to 98% by weight, the catalyst content is 0.1 to 10% by weight, the siloxane oligomer content is 0.1 to 20 parts by weight, The coating composition according to claim 5, wherein the content of the organic solvent is 1 to 10% by weight. The coating composition according to claim 5 or 6, wherein the A material further contains an inorganic pigment. The coating composition of Claim 7 whose content of the said inorganic pigment in the said A material is 10 to 50 weight%. The coating composition according to any one of claims 5 to 8, wherein the content of the A material in the coating composition is 50 to 90% by weight and the content of the B material is 10 to 50% by weight. The coating composition according to any one of claims 1 to 9, wherein the trialkoxysilane compound is at least one selected from the group consisting of alkyltrialkoxysilanes, alkenyltrialkoxysilanes, and aryltrialkoxysilanes. The trialkoxysilane compound has the general formula (3):

[Wherein R ⁹ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a monocyclic or bicyclic aryl group; R ¹⁰ is the same or different and each represents an alkyl having 1 to 6 carbon atoms. Or a monocyclic or bicyclic aryl group. ]
The coating composition in any one of Claims 1-10 which is a compound shown by these. The trialkoxysilane compound includes methyltrimethoxysilane, methyltriethoxysilane, methyltri (n-propoxy) silane, methyltri (i-propoxy) silane, methyltri (n-butoxy) silane, methyl (n-pentoxy) silane, methyl (N-hexoxy) silane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri (n-propoxy) silane, ethyltri (i-propoxy) silane, ethyltri (n-butoxy) silane, ethyltri (n- Pentoxy) silane, ethyl (n-hexoxy) silane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (n-propoxy) silane, n-propyltrimethoxysilane, n-pro Lutriethoxysilane, n-propyltri (n-propoxy) silane, n-propyltri (i-propoxy) silane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri (n-propoxy) silane , I-propyltri (i-propoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, allyltri (n-propoxy) silane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri (n- Propoxy) silane, n-butyltri (i-propoxy) silane, n-butyltri (n-butoxy) silane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-pentyltriethoxysilane, n- Pentilly (i-propoxy) sila N-pentyltri (n-butoxy) silane, n-pentyltri (n-pentoxy) silane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyl (n-propoxy) silane, cyclopentyl (i-propoxy) silane, cyclopentyltri ( n-butoxy) silane, cyclopentyltri (n-pentoxy) silane, cyclopentyltricyclopentoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltri (n-propoxy) silane, n-hexyltri ( i-propoxy) silane, n-hexyltri (n-butoxy) silane, n-hexyltri (n-pentoxy) silane, n-hexyltri (n-hexoxy) silane, cyclohexyltrimethoxysilane, Cyclohexyltriethoxysilane, Cyclohexyltri (n-propoxy) silane, Cyclohexyltri (n-butoxy) silane, Cyclohexyltri (n-pentoxy) silane, Cyclohexyltri (n-hexoxy) silane, Cyclohexyltricyclohexoxysilane, Phenyltrimethoxy Silane, phenyltriethoxysilane, phenyltri (n-propoxy) silane, phenyltri (n-butoxy) silane, phenyltri (n-pentoxy) silane, phenyltri (n-hexoxy) silane, phenyltri (n-hexoxy) The coating composition according to any one of claims 1 to 11, which is at least one selected from the group consisting of silane and phenyltri (phenoxy) silane. The paint according to any one of claims 1 to 12, wherein the inorganic filler is at least one selected from the group consisting of silica, alumina, titania, zirconia, zinc oxide, silicon carbide, silicon nitride, iron oxide and mica. Composition. The coating composition according to any one of claims 1 to 13, wherein the catalyst is at least one selected from the group consisting of formic acid, acetic acid, propionic acid, acrylic acid, hydrochloric acid, sulfuric acid, and nitric acid. The coating composition according to any one of claims 1 to 14, wherein the siloxane oligomer (1) further has an alkyl-substituted alkoxysiloxane structure and / or a dialkylsiloxane structure. The siloxane oligomer (1) has the general formula (1):

[Wherein R ^{1 to} R ⁵ are the same or different and each represents an alkyl group; X is a linear, branched or cyclic silicon-containing group; a is an integer of 1 to 130; b is an integer of 0 to 65; c Is an integer from 0 to 155. ]
Is a compound having a molecular weight of 12000 or less,
The siloxane oligomer (2) has the general formula (2):

[Wherein, R ^{6 to} R ⁸ are the same or different and each represents an alkyl group; d is an integer of 1 to 155. ]
The coating composition in any one of Claims 1-15 which is a compound shown by these. The coating composition according to any one of claims 1 to 16, wherein the organic solvent is an alcohol. The paint according to claim 17, wherein the alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-2-propanol. Composition. The inorganic pigment includes Cr ₂ O ₃ , Fe ₂ O ₃ , TiO ₂ , CuCr ₂ O ₄ , Cu (Cr, Mn) ₂ O ₄ , Cu (Fe, Mn) ₂ O ₄ , Co (Fe, Cr) _2. The coating composition according to claim 3, which is at least one selected from the group consisting of O ₄ , CoAl ₂ O ₄ , Co ₂ TiO ₄ , and silica black. The coating composition according to any one of claims 1 to 19, which is a composition for the outermost surface of a roller, a mold, a plate, a chute, a hopper, or a cooking utensil. The coating film using the coating composition in any one of Claims 1-20. The coating film according to claim 21, wherein the thickness is 5 μm or more. The coating film according to claim 21 or 22, which is a coating film for an outermost surface of a roller, a mold, a plate, a chute, a hopper, or a cooking utensil. The member for outermost surfaces of a roller, metal mold | die, plate, chute | shoot, hopper, or a cooking utensil which consists of a coating film in any one of Claims 21-23. A roller, a mold, a plate, a chute, a hopper, or a cooking utensil comprising the outermost surface member of the roller, mold, plate, chute, hopper, or cooking utensil according to claim 24 on the outermost surface.