JPH02229837A - Surface treating agent - Google Patents

Abstract

PURPOSE:To obtain a surface treating agent, consisting of polyorganosiloxanes, a polyurethane resin and powder and capable of imparting lubricity, abrasion resistance, etc., to surfaces of rubbers or plastics by application thereto. CONSTITUTION:A surface treating agent consisting of (A) 100 pts.wt. polyol having >=2 OH groups, (B) 0.1-100 pts.wt. polyorganosiloxane having >=2 OH groups bond to Si, (C) 0.1-100 pts.wt. curable substance consisting of a mixture of (C1) a polyorganosiloxane having >=2 monofunctional hydrocarbon groups substituted with epoxy group-containing groups and 10-5000 polymerization degree with (C2) a silane and/or siloxane having amino groups and alkoxy groups bound to Si and/or a partial reaction product thereof, (D) 10-1000 pts.wt. polyfunctional isocyanate, (E) 0.01-100 pts.wt. metal compound, (F) 0.1-1000 pts.wt. powder having 0.1-200mum average particle diameter and (G) an organic solvent.

Description

[Detailed Description of the Invention] [Objective of the Invention] (Industrial Application Field) The present invention is applied to the surface of rubber or plastics and cured to give the surface lubricity, abrasion resistance, and water repellency. , relates to a surface treatment agent suitable for imparting non-freezing properties, non-sticking properties, chemical resistance, etc.

(Prior art) For example, weather strips used in automobiles, glass run consisting of a glass run inner and glass run outer that support window glass from the inside and outside, glass run channels that support sliding window glass, gaskets such as building sashes, etc. Usually, rubber, soft polyvinyl chloride resin, etc. are mainly used. By the way, the above-mentioned glass runs, gaskets, etc. are treated to reduce the sliding resistance of the sliding parts so that they can withstand the sliding movement and attachment to and removal from glass and painted panels that occur when windows and doors are opened and closed. . For example, in the sliding part (a
) Fibers such as polyamide resin are electrostatically flocked or brushed, or (b) fine powders of polyamide resin, fluororesin, beads of polystyrene resin, metal or silicon carbide are added to urethane paint, which basically consists of polyol and isocyanate. or a mixture of silicone oil and at least one selected from the group of oxides, molybdenum disulfide, and metal soaps, (C) silicone oil, (d)
A curable silicone paint, (e) a mixture of urethane paint and curable silicone, is applied to the surface of a base material made of rubber, soft polyvinyl chloride resin, etc. to reduce the contact area of the surface or to make the surface slippery. Measures are being taken to provide this.

(Problems to be Solved by the Invention) However, each of the means (a) to (e) above has the following problems. That is, in the case of the method (a) in which the sliding resistance is lowered by electrostatic flocking or raising of the fibers, there is a problem in the working environment for the electrostatic flocking or raising. Also, for example, Japanese Patent Publication No. 57-14986 and Japanese Patent Publication No. 82-1
In the case of (b) disclosed in Publication No. 2262, etc., the required slipperiness cannot be sufficiently imparted to the surface, and for example, when applied to a glass run for a vehicle, a loud noise is generated due to sliding of the glass. There are some drawbacks. Moreover, since the abrasion resistance is poor and the compatibility between the silicone oil and the urethane paint is also poor, the silicone oil oozes out and is easily washed away by dust or rainwater, and the lubricity effect is temporary. Furthermore, when fluororesin powder or plastic particles are dispersed and contained in the urethane paint, not only is it necessary to stir the paint appropriately to form a homogeneous paint film, but also the formed paint film becomes sticky. It is disadvantageous in that it is inferior in aqueous properties, non-sticking properties, and non-freezing properties, and is also inferior in sliding properties and durability. Furthermore, in the case of (c), the added lubricity is only temporary because dust adheres to the coated silicone oil layer or the silicone oil layer itself is washed away by rain or the like. Moreover, when applied to a glass run, there is also the disadvantage that silicone oil migrates and adheres to the sliding glass surface, obstructing visibility. Furthermore, for example,
In the case of (d) disclosed in JP-A-6-19813, JP-A-61-159427, etc., polydiorganosiloxane with silanol at both ends, polydimethylhydride dienesiloxane, epoxy group-containing polydiorganosiloxane, When using a curable silicone containing an amino group and an alkoxy group bonded to a silicon atom as essential components, boridiorganosiloxane and an organometallic fatty acid salt as a catalyst are used, the cured silicone coating formed on the surface is the base material. It has selectivity in terms of density and youthfulness. for example,
It does not substantially adhere to rubber or soft polyvinyl chloride resin, and it does not adhere to plastics containing plasticizers, so if the glass surface contacts and slides under relatively strong pressure, such as in glass run, the coating film will not adhere. There is a problem that the strength is insufficient and the durability is inferior. Furthermore, even if they are in close contact, the coating may break and fall off if the glass end surfaces contact and slide under relatively strong pressure, such as in a glass run. On the other hand, for example, JP-A-61
In the case of (e) disclosed in JP-A-138838 to JP-A-61-13H39, etc., urethane paint is coated with curable silicone, such as polydiorganosiloxane with silanol groups at both ends, polymethylhydrodiene siloxane, and catalyst. When an organometallic fatty acid salt is added and blended, high temperature or long time is required for curing the silicone, so it is not suitable for surface treatment of base materials with low heat resistance such as polyvinyl chloride resin. Moreover, the hydrogen atoms bonded to the silicon atoms of polymethylhydrogensiloxane easily react with the silanol groups (hydroxyl groups bonded to silicon atoms) of polydiorganosiloxane, so the isocyanate groups and silanol groups in the urethane paint are easily reacted. reaction is inhibited. In other words, the coating film formed is simply a mixture of cured polyurethane and cured silicone, and since these two are not compatible, it is difficult to apply it to glass run channels where glass is slid with strong force. The silicone content is removed and the lubricity is reduced or eliminated.

In addition, attempts have been made to incorporate modified silicone oils having functional groups at both ends that react with isocyanates into urethane paints (Japanese Patent Publication No. 4408/1983). In this case, a polyurethane coating containing diorganosiloxane blocks is formed, improving water repellency and non-sticking properties, but it is difficult to apply to glass run channels etc. where glass slides due to poor lubricity. . Furthermore, attempts have been made to reduce frictional resistance by adding lubricants such as silicone oil to polyvinyl chloride resin (JP-A-Sho H-
6045) cannot be considered to be a fully satisfactory means for improving and improving slipperiness.

[Structure of the Invention] (Means for Solving the Problems) The present invention has been made in response to the above-mentioned circumstances. Polyorganosiloxanes with excellent water repellency, non-freezing and non-stick properties, polyurethane resins with excellent adhesion to polymeric materials, abrasion resistance and chemical resistance, and improved lubricity. The main idea is to combine powders (particles) that contribute to improvements, etc., and to fully utilize the mutual properties (features) of each of these components. That is, the present invention comprises 100 parts by weight of a polyol having at least two hydroxyl groups in one molecule, and 0.1 to 0.1 parts by weight of a polyorganosiloxane having at least two silicon-bonded hydroxyl groups in one molecule.
100 parts by weight, (a) General formula (R゜) SiO(4-a)/2a (wherein R' is the same or different and selected from a hydrogen atom and a monovalent substituted or unsubstituted hydrocarbon group) Indicates a monovalent group, at least 291 of all R's in one molecule are monovalent hydrocarbon groups substituted with an epoxy group-containing group, a is 1-
A polyorganosiloxane having a degree of polymerization of IO to 5.000 and consisting of a structural unit represented by (representing an integer of 3), and (1) a substituted or unsubstituted amino group bonded to a silicon atom through at least one carbon atom. and a silane and/or siloxane having an alkoxy group bonded to a silicon atom, so that the number of amino groups in the epoxy group-containing group 1 (II) in (a) is 0.1 to 10. 0.1 to 100 parts by weight of a curable substance which is a mixture blended with or a partial reaction product thereof or a mixture of the above partial reaction product and (a) and/or (i), polyvalent isocyanate lO~ 1,000 parts by weight, 0 metal compounds
．． 01-100 parts by weight, average particle size 0.1-200
This is a surface treatment agent characterized by comprising 0.1 to 1.000 parts by weight of μ layer powder and a 9-layer solvent.

(Function) According to the present invention, polyorganosiloxanes have excellent lubricity and water repellency. Non-freeze and non-stick properties, excellent adhesion of polyurethane resin to polymeric materials, as well as abrasion resistance, chemical resistance, and improved lubricity of powder (particles) make it easy to use. , excellent wear resistance required over a long period of time. It can form a coating film (coating layer) that is water repellent, non-freezing, non-stick, and chemical resistant.

(Example) Examples of the present invention will be described below. First, the reasons for selecting each component and composition ratio of the surface treatment agent according to the present invention will be explained.

<Regarding the polyol component having at least two hydroxyl groups in one molecule> This polyol component is the main component forming the polyurethane coating, and any compound that can be used as a raw material for producing a polyurethane resin can be used.

That is, polyethylene glycol. Polyoxyalkylene glycols such as polybrobylene glycol, polytetramethylene glycol, and copolymers of polyethylene glycol and polypropylene glycol, polyhydric alcohols such as glycerin, or compounds with two or more amino groups and alkylene oxides. or polyether polyols obtained from the above-mentioned hydroxy group-containing compounds, and adipic acid, maleic anhydride, fumaric acid, succinic anhydride, itaconic acid. Polyester polyols obtained by reacting with polybasic acids such as sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and pyromellitic anhydride, polylactone ester polyols obtained by ring-opening ε-cabrolactam, and hydroxyl at the terminals. It is obtained by chain-extending a low-molecular-weight diamine to a urethane polyol that has a hydroxyl group at the end, which is a reaction product between a polyol containing a polyol and an isocyanate, or a urethane polymer, which is a reaction product between a polyol and isocyanate 1. Examples include urethane polymers having amino groups at the ends. Of these, polyester polyols and urethane polyols having a hydroxyl group at the end are particularly preferred.

<Regarding the polyorganosiloxane component having at least two hydroxyl groups bonded to silicon atoms in one molecule width> Due to the reactivity of the hydroxyl group, this component has substituted or unsubstituted hydroxyl groups bonded to the silicon atom via at least one carbon atom. It reacts with the alkoxy groups of silanes and siloxanes that have substituted amino groups and alkoxy groups bonded to silicon atoms to form a polyorganosiloxane film, which serves to impart water repellency, non-stick properties, etc. to the coating film. . In this component, organic groups bonded to silicon atoms other than hydroxyl groups include alkyl groups such as methyl, ethyl, probyl, butyl, and hexyl groups, and vinyl groups. Alkenyl groups such as allyl groups, aryl groups such as phenyl groups, aralkyl groups such as styrenyl groups, and some of the hydrogen atoms of these hydrocarbon groups are replaced by fluorine atoms,
Examples include substituted hydrocarbon groups substituted with chlorine atoms, nitrile groups, etc. A methyl group is preferred from the viewpoint of ease of synthesis, ease of handling, and curing speed at room temperature. In addition, the viscosity of this polyorganosiloxane component is 2
500 to 50,000,000 cSt, preferably 600 to 20,000 cSt at 5°C. 000cSt. That is, if the viscosity is too low, the cured coating will become brittle, and if the viscosity is too high, it will be inconvenient to handle as a surface treatment agent.

In the present invention, the composition ratio of this polyorganosiloxane component is from 0.1 to 100 parts by weight of the polyol component.
The amount is selected within the range of 100 parts by weight. In other words, if the amount is less than 0.1 parts by weight, there is no effect of adding it, and if it is more than 100 parts by weight, the adhesion to the substrate will decrease, the formed coating will be uneven, the wear resistance will be impaired, and the product will be damaged. It is.

<(A) Regarding the one (1) type curable substance component> General formula
Polyorganosiloxane represented by (R゛) SiO(4-a)/2a is a monovalent hydrocarbon water substituted with at least two epoxy group-containing groups in one molecule; Examples of the containing group include a glycidoxy group and a 3,4-oxycyclohexyl group. R' other than these eboxidized hydrocarbon groups
Examples include methyl group, ethyl group, and proyl group. Butyl group. Alkyl groups such as hexyl groups, alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups, aralkyl groups such as styrenyl groups, and some of the hydrogen atoms of these hydrocarbon groups are replaced by fluorine atoms, Examples include substituted hydrocarbon groups substituted with chlorine atoms, nitrile groups, etc. Further, the terminal end is usually closed with a triorganosilyl group, but it may contain a hydroxyl group bonded to a silicon atom. From the viewpoint of ease of synthesis, ease of handling, mechanical strength of the final coating film, etc., the degree of polymerization of the polyorganosiloxane is approximately 10 to 5,000, preferably 50 to 1,000. Selected within the range of 000.

On the other hand, silanes and siloxanes are silanes having a substituted or unsubstituted amino group bonded to a silicon atom through at least one carbon atom and an alkoxy group bonded to a silicon atom, and are obtained by partial condensation of these silanes. siloxane, also L. The preferred is a polysiloxane obtained by an equilibration reaction between the silane and a cyclic polyorganosiloxane. Examples of the substituted or unsubstituted amino group include aminomethyl group, β-aminoethyl group, γ-aminopropyl group, and δ-aminobutyl group. γ-1(methylamino)probyl group, γ-1(ethylamino)probyl group.
Examples include γ-(β-aminoethylamino)probyl group and salts obtained by converting some or all of these amino groups into quaternary ammonium. Therefore, from the viewpoint of stability during storage, it is preferable that the amino group is bonded to the silicon atom through at least three carbon atoms, such as a γ-aminobutylene group. The silanes and siloxanes are selected from those having at least one group containing the substituted or unsubstituted amino group in one molecule, and further having an alkoxy group bonded to a silicon atom. These alkoxy groups include methoxy and ethoxy groups. Examples include bropoxy group and butoxy group, but methoxy group and ethoxy group are common from the viewpoint of ease of synthesis, and it is preferable that one molecule contains at least two alkoxy groups.

Therefore, the above-mentioned (a) component and (l) component are selected to have the following composition ratio. That is, for each epoxy group-containing group in the polyorganosiloxane of component (A), (
(1) The amino group bonded to the silicon atom through at least one carbon atom of the component silane or siloxane is 0.
．． The number is selected to be 1 to 10 pieces, preferably 0.7 to 2.5 pieces. If the number of amino groups is outside the above range, the curability and adhesion to the substrate will be insufficient, and if the number of amino groups is too large, the curability will be poor and the mechanical strength of the coating film formed will be reduced. In addition, these (a) component and (b) component are generally used in the form of a mixture, but these partial reaction products or the above partial reaction product and (b) component and/or
Alternatively, it may be used in the form of a mixture with (oral) ingredients.

In the present invention, the composition ratio of component (a) to component (0) is from 0.1 to 100 parts by weight of the polyol component.
Selected as 1aO flea weight section. The reason for this is that if it is less than 0.1 part by weight, it will not have the effect of imparting lubricity to the formed coating film, and if it is more than 100 parts by weight, the stability of the surface treatment agent will be impaired and the coating operation will become difficult.

Regarding the polyvalent isocyanate component> This component is a compound having at least two isocyanates M in one molecule, and all the compounds used as raw materials when producing ordinary polyurethane resins can be used.

That is, the basic ingredients of polyurethane resin are compounds commonly called diisocyanates, such as tolylene diisocyanate, diphenylmethane diisocyanate, dianisidine diisocyanate, diphenyl ether diisocyanate, bitolylene diisocyanate, naphthalene diisocyanate, and hexamethylene diisocyanate.
Isophorone diisocyanate, lysine diisocyanate methyl ester, metaxylene diisocyanate. 2
, 2,4-trimethylhexamethylene diisocyanate
Examples include dimer acid diisocyanate, isobropylidene bis(4-cyclohexyl isocyanate), cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, and tolylene diisocyanate dimer. Furthermore, triphenylmethane triisocyanate, triisocyanate phenylthiophosphate, biuret or cyanurate forms of the above diisocyanates, adducts of the above diisocyanates and polyhydric alcohols such as trimethylolbroban, etc.
Compounds having more than one isocyanate group may also be mentioned. In addition, any compound having two or more isocyanate 1 residues which is a brevolimer of the above-mentioned isocyanate group-containing compound and a polyhydric alcohol or a compound having two or more amino groups can be used. Blocked isocyanates in which the groups are blocked with active hydrogen-containing compounds such as phenols, oximes, lactams or sodium bisulfate can also be used.

In the present invention, the component ratio of this polyvalent isocyanate component is 1{.~t per ioo parts by weight of the polyol component.
．． The reason why ooo parts by weight was selected is as follows.

In other words, the hydroxyl group obtained by ring-opening of the epoxy group contained in this component, the amount of active hydrogen in the NH group after the reaction between the epoxy group and the amino group, and the amount of excess amino group in the component. The appropriate amount is determined according to t. This is because if the amount exceeds 0.000 parts, foaming etc. will be observed in the formed coating film and the required slipperiness will not be imparted.

<About metal compound components> This component is a polyol component, a polyorganosiloxane component, and a (a)-(b) component system. It plays the role of promoting the reaction between silanol groups, hydroxyl groups, and alkoxy groups in the polyvalent isocyanate component system, and coloring the formed coating film.

Types of metals include iron and zinc. nickel, cobalt,
Examples include lead, tin, and aluminum.

In addition, examples of metal compounds include oxides, hydroxides, and chlorides. Examples include inorganic compounds such as phosphates, organic acid salts such as acetate and octate, chelate compounds, or organometallic compounds and organic acid salts bonded to backbone groups such as butyl and octyl groups. may be used alone or in a mixed system of two or more. Furthermore, as metals, iron, zinc,
Tin and the like are preferred, and oxides are recommended as the compound.

In the present invention, the composition ratio of this metal compound is selected within the range of 0.01-too parts by weight per 100 parts by weight of the polyol component. Here, if the strain amount is less than 0.01 parts, the effect of promoting the reaction is insufficient, and if the strain amount is less than 10 parts
This is because if the amount is more than 0 parts by weight, the formed coating film may be discontinuous, resulting in poor durability.

About the powder component with an average particle size of 0.1 to 200μ〉This component contributes to improving lubricity, etc., and is suitable for use with inorganic and organic pigments, metal carbides or oxide powders, and metal soaps. Powder, polyamide resin powder. Fluororesin powder. Examples include sulfide powder and silicone resin powder. Specifically, carbide powders include titanium carbide, tantalum carbide, and zirconium carbide. Barium carbide, niobium carbide, chromium carbide. Powders such as molybdenum carbide, silicon carbide, tungsten carbide, and aluminum oxide as oxides. Examples include powders such as titanium oxide and silicon oxide. On the other hand, examples of polyamide resin powder include nylon G6, nylon 6lO, nylon 6, nylon 11,
There are powders such as nylon 12 (all trade names), and examples of fluororesin powders include powders such as polytetrafluoroethylene, polychlorotrifluoroethylene, and tetrafluoroethylene-hexafluorobrobylene copolymer. . Furthermore, examples of the sulfide powder include powder such as molybdenum disulfide, and examples of the silicone resin powder include powder such as polymethylsilsesquioxane. Among these, polymethylsilsesquioxane powder having a true spherical shape is preferred from the viewpoint of dispersion stability and imparting lubricity to the formed coating film.

As mentioned above, this component has the function of improving the required lubricity on the formed coating surface by providing a rolling effect and reducing the contact surface area. In order to further improve this function, the powder component may contain silicone oil and may be used in combination. In this case, the silicone oil includes dimethyl silicone oil, methylphenyl silicone oil, silicone oil in which the organic group bonded to the silicon atom is substituted with an alkyl group other than methyl group, a part of the organic group is fluorine atom, chlorine atom, Examples include silicone oils substituted with nitrile groups, epoxy groups, acryloxy groups, etc. In general, dimethyl silicone oil is preferred due to its synthetic properties, and its viscosity is 10 to 100 t. 000.0
00 cst is sufficient, but considering durability and ease of handling, to. ooo~50G. 0(10cs
It is preferable that the thickness be about t.

In the present invention, this component is 100% of the polyol component 100
Per weight part: 0.1 to 1.000 parts by weight, preferably 1 to 1.000 parts by weight
Select within the range of 400 parts by weight. That is, if the amount is less than 0.1 part by weight, the effect of addition, that is, the durability of slipperiness, is not observed, and t. This is because if the weight exceeds the weight limit, the coating film formed will have no flexibility, will have poor adhesion to the substrate, and will have poor durability.

Furthermore, for this component, the average particle size is 0.1 to 200.
The reason why we chose μm is that if it is less than 0.1 μm, it will not have the effect of lowering the coefficient of friction, and if it is more than 2 (10 μm, the formed coating film will not be able to retain this powder, but it will come off, and it will not have the effect of imparting lubricity. This is because it cannot be done.

About the organic solvent component> This component dissolves or disperses each of the above-mentioned components, making it easier to handle as a surface treatment agent (adjusting the viscosity to make treatment operations easier), and also imparting storage stability (stability) to the surface treatment agent. It is something that involves. Therefore, examples of the Bfi solvent include aromatic solvents such as toluene and xysilene, chlorinated hydrocarbon solvents such as 1,1.1-}licroethane, or combinations of these solvents and ketones such as methyl ethyl ketone and methyl isobutyl ketone. Examples include mixed solvents with butyl acetate and butyl acetate.

In the present invention, the amount is selected within the range of about 10 to 2,000 parts by weight per 100 parts by weight of the polyol component.

In other words, if it is less than 10 parts by weight, it cannot provide the required storage stability (stability), and if it is more than 2,000 parts by weight, the coating film formed is so thin that it must be repeatedly coated to provide the desired function. This is because the operations become complicated.

Next, specific examples of the present invention will be explained.

<Preparation of urethane brebolymer> A polyester polyol with a molecular weight of about 2,000 obtained by reacting butanediol and adivic acid, parts by weight, was dissolved in 200 parts by weight of methyl ethyl ketone, 6 parts by weight of tolylene diisocyanate was added, and dibutyl 80°C, 31°C in N2 gas using tin dilaurate as a catalyst.
A non-volatile content som=% solution of a urethane prebolimer having a terminal hydroxyl group obtained by heating for 1r was prepared, and this solution 10
0 parts by weight was diluted with 200 working parts of toluene to obtain a urethane brevolomer solution (U-1).

Preparation of polyorganosiloxane> A polyorganosiloxane with a molecular weight of approximately 50, in which a γ-glycidoxib group and a methyl group are bonded to 1/10 of the silicon atoms in the siloxane molecule, and two methyl groups are bonded to each of the other silicon atoms. Polydimethylsiloxane IOffim part and N-β-
An organosilicon compound obtained by mixing with 10 parts by weight of aminoethyl-3-aminobutyltrimethoxysilane and heating the mixture was dissolved in 8 parts of isobrobyl alcohol to prepare a polyorganosiloxane solution (S-1).

In addition, γ is added to 1/10 of the silicon atoms in the siloxane molecule.
- parts by weight of polydimethylsiloxane IO having a degree of polymerization of about 200, in which a glycidoxibyl group and a methyl group are bonded, and two methyl groups are bonded to each other silicon atom, and 10 parts by weight of γ-aminobrobyltriethoxysilane. When a clear increase in viscosity was observed, the heating was stopped and the resulting organosilicon compound was mixed with isobrobyl alcohol 80%.
Polyorganosiloxane solution (S-2
) was prepared.

Furthermore, γ is added to the 175 silicon atoms in the siloxane molecule.
- polydimethylsiloxane xoii part with a degree of polymerization of about 600, in which a glycidoxibyl group and a methyl group are bonded, and two methyl groups are bonded to each other silicon atom, and γ
-Aminopropyltriethoxysila>30. +f
The organosilicon compound obtained by mixing and heating the IM parts was dissolved in 60 parts by weight of isobrobyl alcohol to prepare a polyorganosiloxane solution (S-3).

<Polyvalent isocyanate> Polyisocyanate obtained by the reaction of 3 mol of hexamethylene diisocyanate and trimethylolbroban I + gol (manufactured by Nippon Polyurethane Co., Ltd., Coronate 1)
1L) was prepared.

(Specific Example 1) To 300 parts by weight of urethane brevolimer solution (U-1),
10 parts by weight of polydimethylsiloxane with silanol at both terminals and a viscosity of approximately 800cSL (25°C), average particle size of approximately 2μ
Add 5 parts by weight of polymethylsilssesquioxane powder and 0.5 ffiffi part of zinc octylate from (2), and further add 10 parts by weight of polyorganosiloxane solution (S-1) to prepare a mixed solution, and add polyisocyanate to this mixed solution. A surface treatment agent was prepared by blending 50 parts by weight.

The surface treatment agent prepared above was applied to a soft polyvinyl chloride resin sheet by the dip foot method, and the coating film formed by drying at room temperature was evaluated for strength, adhesion, tactile lubricity, and glass lubricity. All showed excellent performance.

Further, this surface treatment agent was applied to the sliding portion of the glass run base material made of soft polyvinyl chloride resin, and the surface treatment was performed by drying at room temperature. The treated surface of the glass run base material that has been subjected to this surface treatment is pressed against the glass plate surface as shown cross-sectionally in Figure 1, and the resistance when the glass plate is moved forward and backward (JP? movement) and the sound of rubbing at that time. and the effect on the glass plate surface was evaluated. The resistance was light, the scraping sound was small, and no effect on the glass plate surface was observed.

(Specific example 2) Urethane brevolimer solution (U-1) 30
0 parts by weight, 10 parts by weight of polydimethylsiloxane having silanol at both terminals and having a viscosity of approximately 800 cSt (25°C), and 211 parts by weight of tetrafluoroethylene resin powder having an average particle size of approximately 5 μm.
Part I and 2 parts by weight of triiron tetroxide were added, and 10 parts by weight of polyorganosiloxane solution (S-2) were added to prepare a mixed solution.
A surface treatment agent was prepared by blending parts by weight.

The surface treatment agent prepared above was evaluated for coating film (strength, etc.) and for application to glass run using the same methods as in Example 1, and the same results as in Example 1 were obtained. Ta.

(Specific Example 3) Moles of methyltrimethoxysilane, dimethyldimethoxysilane and diphenylsilanediol were added to 300 parts of urethane brevolimer solution (U-1).
10 parts by weight of a cohydrolyzed condensate with a ratio of 5:1:2, 5 parts by weight of polyamide resin (nylon) powder with an average particle size of about 20μ, and 3 parts by weight of triiron tetroxide were added, and a polyorganosiloxane solution ( S-3) 10 parts by weight were added to prepare a mixed solution, and 50 parts by weight of polyisocyanate was blended with this mixed solution to prepare a surface treatment agent.

The surface treatment agent prepared above was evaluated for coating film (strength, etc.) and for application to glass run using the same methods as in Example 1, and the same results as in Example 1 were obtained. Ta.

(Specific Example 4) 300 parts by weight of urethane polymer solution (U-1) was added with a viscosity of about 20. Add 40 parts of polydimethylsiloxane having silanol at both terminals of OQQcSt (25°C), 30 parts by weight of polymethylsilsesquioxane powder with an average particle size of about 0.8 μm, and 0.8 parts by weight of zinc octylate.
Further, 30 parts by weight of polyorganosiloxane solution (S-1) was added to prepare a mixed solution (1), and 200 parts by weight of polyisocyanate was blended with this mixed solution to prepare a surface treatment agent.

Regarding the surface treatment agent prepared above, coating film evaluation (strength, etc.) and evaluation of application to glass runs were performed using the same methods as in Example 1, and the same results as in Example 1 were obtained. It was done.

(Specific Example 5) Urethane blend polymer solution (U-1) 30
0 parts by weight, moles of methyltrimethoxysilane, dimethyldimethoxysilane and diphenylsilanediol (
60 parts by weight of a cohydrolyzed condensate with a ratio of 5=1:2, 20 parts by weight of tetrafluoric ethylene resin powder with an average particle size of about 10 μm, and 5 parts by weight of triiron tetroxide, and further polyorganosiloxane. A mixed solution was prepared by adding 20 parts by weight of Sold(S-3), and 20 parts by weight of polyisocyanate was blended with this mixed solution to prepare a surface treatment agent.

The surface treatment agent prepared above was evaluated for coating film (strength, etc.) and for application to glass run using the same methods as in Example 1, and the same results as in Example 1 were obtained. Ta.

(Specific Example 6) Urethane brevolimer solution (U-1) 30
0 parts by weight, the viscosity is approximately 40.000 cSt (25℃
), 20 parts by weight of polydimethylsiloxane with silanol at both ends, 10 parts by weight of polymethylsilsesquioxane powder with an average particle size of about 1.5 μm, and a viscosity of about 20.000 eSt.
Add 10 parts by weight of polydimethyl silicone oil (25°C) and 0.8 parts by weight of zinc octylate, and further add 30 parts by weight of polyorganosiloxane solution (S-2) to prepare a mixed solution for 7 nights. A surface treatment agent was prepared by mixing 70 parts by weight of polyisocyanate and 100 parts by weight of toluene.

The surface treatment agent prepared above was evaluated for coating film (strength, etc.) and for application to glass run using the same methods as in Example 1, and the same results as in Example 1 were obtained. Ta.

(Comparative example 1) Urethane brevolimer solution (U 1) 300 weight liters
A surface treatment agent was prepared by dispersing 5 parts by weight of polyamide resin (nylon) powder having an average particle size of about 20 μm in 1 part, and adding 50 parts by weight of polyisocyanate thereto.

(Comparative Example 2) Urethane prepolymer solution 3 obtained in the same manner except that 1.1.1-trichloroethane was used instead of toluene as the diluent solvent in urethane prepolymer solution (U-1).
00 parts by weight, average particle size of about 51 lI! A surface treatment agent was prepared by dispersing 15 parts by weight of the tetraphenic ethylene resin powder of No. 1 and blending 50 parts by weight of polyisocyanate therein.

(Comparative Example 3) Urethane bream polymer solution 3 obtained in the same manner except that 1.1.1-trichloroethane was used instead of toluene as the diluent solvent in urethane bream polymer solution M (U-1).
00 parts by weight, 10 parts by weight of dimethyl silicone oil having a viscosity of about 800 cSt (25°C) and an average particle size of about
μ1 tetraph mouth ethylene resin powder 15ffiffi
50 parts by weight of polyisocyanate was mixed therein to prepare a surface treatment agent.

(Comparative Example 4) Urethane prebomer solution (U-1) 30Off1
One part is alcohol-denatured silicone oil (KF 851 manufactured by Shin-Etsu Chemical Co., Ltd.) with a viscosity of approximately 80 cSt (25°C).
) 10 parts by weight and 5 parts by weight of polyamide resin (nylon) powder having an average particle size of about 20 μm are dispersed, and polyisocyanate to! A surface treatment agent was prepared by blending part Iim.

(Comparative Example 5) Degree of polymerization is approximately 2,000 (viscosity at 25°C is approximately 180
．． 00OcSt) and 1.5 parts by weight of polymethylhydrodiene siloxane with a degree of polymerization of about 50 (viscosity at 25°C: about 30 cSt) were dissolved in 100 parts by weight of toluene, and dibutyltin was added to the solution. A surface treatment agent was prepared by mixing 50 parts by weight of a solution prepared by adding 0.1 part by weight of diacetate with 350 parts by weight of a surface treatment agent having the same composition as in Comparative Example 1 above.

(Comparative Example 6) Parts by weight of polydimethylsiloxane IO having both terminal silanol having a degree of polymerization of about 2,000 and 1 part by weight of polymethylhydrogensiloxane having a degree of polymerization of about 50. 5 parts by weight of toluene
100 parts by weight of epoxy 2. A curable silicone solution was prepared by adding 5 parts by weight of silicone oil, 5 parts by weight of γ-aminopyrtriethoxysilane, and 1 part by weight of dibutyltin diacetate, and a surface of the same composition as in Comparative Example 1 was added. A surface treatment agent was prepared by mixing with 350 parts by weight of a treatment agent. After preparation, this surface treatment agent reacted rapidly and became gel-like, unable to function as a paint.

Regarding each surface treatment agent of Comparative Examples 1 to 5, Specific Example 1
(However, in the case of Comparative Example 5, 80
When coating films were formed by heating and drying at 15 ain at It was divided into two types: one in which the membrane had fallen off (Comparative Example 5) and the other in which the membrane had fallen off. In addition, in terms of finger lubricity and glass lubricity, there were cases in which no effect was observed at all (Comparative Example 1), and cases in which almost no effect was observed (Comparative Example 1).
Comparative Example 4), and although the effect was observed, it was not sufficient (Comparative Examples 2 and 3), both of which were inferior to the surface treatment agent according to the present invention. In addition, in the case of Comparative Example 3, migration of silicone oil to the glass plate surface was observed in the evaluation of glass slipperiness.

Furthermore, assuming application to glass run base material, specific example 1
In the same way as in the case of Figure 1, we evaluated the resistance, scraping noise, and effect on the glass plate surface.The resistance was slightly lighter in Comparative Example 3, but the resistance was heavy in all cases, and the rubbing noise was also evaluated. In addition to the case of Comparative Example 3, which is small, there are two types: one that makes a "crusty sound" (Comparative Example 2), and one that makes a "squeaky" sound when it rubs against glass (Comparative Example 1.4).
Regarding the influence on the glass plate surface, in the case of Comparative Example 3, silicone oil film adhesion was observed.

[Effects of the Invention] As described above, the surface treatment agent according to the present invention can easily impart strong and excellent lubricity to the surface of a base material, for example, by treating the surface of a base material made of an elastic polymer. It is possible.

In other words, by treating the surface of the base material and forming a coating film thereon, it is possible to maintain and exhibit excellent and durable sliding properties. Moreover, the coating film formed above has excellent water repellency, non-freezing property, non-stick property, and chemical resistance, so it can be used on various structural materials that require lubricity or sliding properties. It can be said that it is suitable for processing.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing a cross-sectional evaluation example of a surface treated with a surface treatment agent according to the present invention. 1...Surface-treated glass run base material 2...Glass plate

Claims (1)

Scope of Claims: 100 parts by weight of a polyol having at least two hydroxyl groups in one molecule, 0.1 to 1 part of a polyorganosiloxane having at least two silicon-bonded hydroxyl groups in one molecule
00 parts by weight, (a) General formula (R')_aSiO_(_4_-_a_)_/_2 (wherein R' is the same or different and selected from a hydrogen atom and a monovalent substituted or unsubstituted hydrocarbon group) A structural unit represented by a monovalent group, at least two of all R' in one molecule are monovalent hydrocarbon groups substituted with epoxy group-containing groups, a is an integer from 1 to 3) (b) a silane having a substituted or unsubstituted amino group bonded to a silicon atom through at least one carbon atom and an alkoxy group bonded to a silicon atom; and/or siloxane such that the number of amino groups in (b) is 0.1 to 10 per one epoxy group-containing group in (a), or a partial reaction product of these or 0.1 to 100 parts by weight of a curable substance that is a mixture of the partial reaction product and (a) and/or (b), 10 to 1,000 parts by weight of a polyvalent isocyanate, and 0.01 to 100 parts by weight of a metal compound. parts, powder with an average particle size of 0.1 to 200 μm 0.1 to 1,00
A surface treatment agent comprising 0 parts by weight and an organic solvent.