JPH0778196B2 - Surface modification composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a basicity of a polysiloxane graft polymer obtained by polymerizing a monomer mixture containing a polymerizable silane compound in the presence of a terminal hydroxyl group-containing polysiloxane. An aqueous dispersion of a salt with a compound, or a surface-modifying composition comprising the aqueous dispersion and a water-soluble resin, which is applied to the surface of a substrate such as a film, a fiber or a steel plate,
The present invention provides a composition that imparts surface properties such as water repellency, slipperiness, heat resistance, peeling resistance, and migration resistance.

[Conventional technology]

In recent years, demands for performance of magnetic tapes, floppy disks, thermal printing materials, etc. such as slipperiness, heat resistance, and abrasion resistance have become more and more sophisticated with the development of electronic devices.
The emergence of compositions that meet these requirements is sought.
In order to meet the requirements for slipperiness, heat resistance, wear resistance, etc.,
Various improvements have been made in the past. These methods are roughly classified into two directions: modification of a film body used as a base material of a magnetic tape or a thermal printing material, and modification by coating a modifying substance on the surface.

As the former method, a method using a heat resistant resin film such as polymide or polysulfone as a substrate (Japanese Patent Laid-Open No. 59-1528).
No. 94) is disclosed, but it is expensive and it is difficult to obtain a thin film required for high functionality.

In the case of polyester film most commonly used as a substrate, a method of forming inorganic particles during polyester production (Japanese Patent Publication No. 34-5144) or a method of adding inorganic particles such as silica or calcium carbonate (Japanese Patent Publication No. 42-
No. 24099, Japanese Examined Patent Publication No. 43-12013) and the like disclose methods for obtaining a film having good slipperiness. However, these methods are difficult to control the particle size of generated particles and are not suitable for obtaining slipperiness. Since it is necessary to add a large amount of inorganic particles, there is a problem in making the film thin and transparent. Furthermore, a method of introducing a terminal hydroxyl group-containing polysiloxane into the polyester main chain (Japanese Patent Laid-Open No. 59-168027) is also disclosed, but a large amount is required because the polysiloxane is distributed throughout the substrate, and the magnetic film is also used. Alternatively, the adhesion of the ink layer also causes a problem.

As the latter method, a method of coating the surface of the substrate with a silicone resin, an epoxy resin, a melamine resin, a fluororesin or the like to modify the surface (US Pat. No. 4310600, JP-B-59-39308).
JP-A-55-7467), but there is a drawback that properties for improving slipperiness, heat resistance and the like and adhesion of the resin coating to the substrate are not compatible. Further, a method of using silicone graft copolymerization using an acrylic-modified silicone (JP-A-58-154766, JP-A-58-164656) is disclosed, and it is possible to achieve both slipperiness and adhesion. But,
The problem remains that the production of acrylic modified silicone is complicated and expensive.

[Problems to be solved by the invention]

The present invention solves the above-mentioned problems of the prior art, retains adhesion to a substrate by a simple method, and provides a slippery, heat-resistant, and wear-resistant surface, while the present inventors Akira
No. 61-215629 proposes a surface modification composition containing a polysiloxane graft polymer obtained by polymerizing a monomer mixture containing a polymerizable silane compound in the presence of a polysiloxane containing a terminal hydroxyl group. However, although the coating film obtained from this surface-modified composition has various properties which are sufficiently satisfactory depending on the use conditions, in some cases, higher heat resistance was required. Also,
It is a surface-modifying composition that substantially contains a solution of a polysiloxane graft polymer in an organic solvent, and its use is restricted as a coating material for the in-line coating method of polyester film, and there are problems in terms of occupational health in use. In addition, depending on the composition of the polymer, there may be a problem that gelation occurs during long-term storage.

Further, as an aqueous dispersion of a polysiloxane graft polymer that has been proposed so far, a vinyl polymer having a carboxyl group and a hydroxyl group is produced in a water-dilutable organic solvent, and a hydroxyl group or an alkoxyl group is added to the vinyl polymer. A water dispersion obtained by reacting an organopolysiloxane having
388) or an organopolysiloxane having a polymerizable unsaturated group and another vinyl-based monomer in an aqueous medium by emulsion polymerization in the presence of an emulsifier (JP-A-51-146525).
No.) is known. However, in these methods, since the organopolysiloxane has low reactivity, modification is often incomplete, and in some cases, phenomena such as separation and aggregation easily occur during the reaction. Therefore, it is a fact that the composition is restricted in order to stably obtain the polysiloxane graft polymer aqueous dispersion having the excellent performance.

[Means for solving problems]

In view of such circumstances, the present inventors have earnestly studied a surface-modified composition which is excellent in water repellency, slipperiness, heat resistance, peeling property, migration resistance, and has no problem of occupational hygiene in use. As a result, the present invention has been reached.

That is, in the present invention, in the presence of 1 to 20% by weight of the terminal hydroxyl group-containing polysiloxane (A), 0.05 to 10% by weight of the polymerizable silane compound (B), 1 to 30% by weight of the unsaturated organic acid (C) and Other polymerizable monomer (D) copolymerizable with
40 to 97.95% by weight (however, the total of the components (A), (B), (C) and (D) is 100% by weight) of a polymer obtained by polymerizing in an organic solvent other than alcohol. An aqueous dispersion of a salt of a polysiloxane graft polymer with a basic compound and a water-soluble resin obtained by stirring a liquid material obtained by adding a basic compound and water to a solution,
0 to 50 of the water-soluble resin per 100 parts by weight (solid content conversion)
The present invention relates to a surface modification composition which is contained in a ratio of parts by weight.

The terminal hydroxyl group-containing polysiloxane (A) used in the present invention can be used without limitation as long as it is a linear or partially branched branched polysiloxane having at least one of the terminals being a hydroxyl group. Can be easily obtained and can be used according to the purpose.

Such a terminal hydroxyl group-containing polysiloxane (A)
For example, the general formula (However, R ₁ and R ₂ are each independently a monovalent hydrocarbon group which may be halogen-substituted, R ₃ is hydrogen or a monovalent hydrocarbon group which may be halogen-substituted, and n is 1 or more. The linear polysiloxane represented by the formula (1) is an integer, but a branched polysiloxane partially branched can also be preferably used.

More specifically, for example, dialkylpolysiloxanes such as dimethylpolysiloxane and methylethylpolysiloxane, alkylarylpolysiloxanes such as methylphenylpolysiloxane, and diarylpolysiloxanes such as diphenylpolysiloxane. And a mixture of one or more selected from these groups can be used.

Among them, a linear or partially branched branched dimethylpolysiloxane having at least one hydroxyl group at the terminal can be obtained at low cost, and a polysiloxane graft polymer having excellent performance can be obtained, which is preferable.

The average molecular weight of the polysiloxane (A) used is
The range of 5 to 1.5 million, preferably 5000 to 1.5 million, and more preferably 20,000 to 1.5 million is desirable.
If the average molecular weight is less than 500, the resulting surface-modified composition may not sufficiently exhibit desired surface properties, and,
If the average molecular weight exceeds 1,500,000, the viscosity becomes high and handling and polymerization operations may be difficult.

The amount of the terminal hydroxyl group-containing polysiloxane (A) to be used can be appropriately determined within the range of 1 to 20% by weight depending on the degree of surface characteristics. If the amount used is less than 1% by weight, the surface properties will not be sufficient, and if it exceeds 20% by weight, the adhesion to the substrate will decrease, which is not desirable.

The polymerizable silane compound (B) used in the present invention is a compound having at least one polymerizable unsaturated group and at least one group capable of undergoing a condensation reaction with the polysiloxane in the molecule, and examples thereof include vinyltriene. Methoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris (β-methoxyethoxy) silane, allyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane , Γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethylethoxysilane, γ- (meth) acryloxypropyltris (β-methoxyethoxy) silane,
2-styrylethyltrimethoxysilane, (meth) acryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, vinyltriacetoxysilane, vinyltrichlorosilane and the like can be mentioned, and one kind selected from these groups or Mixtures of two or more can be used.

The amount of the polymerizable silane compound (B) used can be appropriately determined within the range of 0.05 to 10% by weight. If the amount used is less than 0.05% by weight, the bond between the polysiloxane (A), the polymerizable silane compound (B), the unsaturated organic acid (C) and the polymer composed of the polymerizable monomer (D) is insufficient. Therefore, an effective amount of graft reaction does not occur, and after the aqueous dispersion is formed, unreacted polysiloxane tends to cause layer separation. Also, 10% by weight
If it exceeds the range, the stability becomes poor and gelation during polymerization tends to occur.

The unsaturated organic acid (C) used in the present invention has a function of inducing a bond between the polysiloxane (A) and the polymer to smoothly promote the graft reaction, and at the same time, disperses the resulting polysiloxane graft polymer in water. It is a component for imparting properties, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, and unsaturated such as vinyl sulfonic acid, sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid. Sulfonic acid and the like can be mentioned, and one kind or a mixture of two or more kinds thereof can be used.

The amount of unsaturated organic acid (C) used can be appropriately determined within the range of 1 to 30% by weight, preferably 3 to 20% by weight. 1
If the amount used is less than wt%, it will be difficult to obtain a stable aqueous dispersion, and if it exceeds 30 wt%, the hydrophilicity of the polymer obtained will be too strong, making stable dispersion in water difficult. In addition, the resulting surface modified composition has poor water resistance.

Examples of the polymerizable monomer (D) used in the present invention include acrylic acid esters such as butyl acrylate and 2-ethylhexyl acrylate; 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid 2 -(Meth) acrylic acid hydroxyalkyl esters such as hydroxypropyl; methacrylic acid esters such as methyl methacrylate and butyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatics such as styrene and vinyltoluene Vinyls; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated amides such as acrylamide and N-methylolacrylamide; α-olefins such as ethylene, propylene and isobutylene;
Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and t-butyl vinyl ether; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; (meth) acrylic acid trifluoro Fluorine-containing (meth) acrylic acid esters such as ethyl, 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate An aromatic fluorine-containing (meth) acrylic acid ester such as 2,3,5,6-tetrafluorophenyl acrylic acid ester and 2,3,4,5,6-pentafluorophenylmethacrylic acid ester; These 1 type, or 2 or more types of mixture can be used.

The amount of the polymerizable monomer (D) used can be appropriately determined within the range of 40 to 97.95% by weight. Less than 40% by weight or
When the amount used exceeds 97.95% by weight, the amount of the polysiloxane (A), the polymerizable silane compound (B) or the unsaturated organic acid (C) used is too much or too little compared with the above range, which causes the above-mentioned drawbacks. Is expressed, which is not desirable.

The organic solvent that can be used during the polymerization can be used without limitation as long as it is an organic solvent other than alcohol, that is, an organic solvent having no alcoholic hydroxyl group,
For example, toluene, xylene, benzene, hexane, cyclohexane, trichloroethane, methyl ethyl ketone, ethyl acetate, dioxane, cellosolve acetate and the like can be mentioned, and one kind or a mixture of two or more kinds thereof can be used. Toluene and xylene are particularly preferable in terms of solubility, boiling point and the like.

An alcoholic organic solvent having an alcoholic hydroxyl group, for example, methyl alcohol, ethyl alcohol,
Alcohols such as isopropyl alcohol, and cellosolves such as methyl cellosolve and ethyl cellosolve are prepared from polysiloxane (A) and polymerizable silane compound (B), unsaturated organic acid (C) and polymerizable monomer (D) components. It cannot be used from the beginning of the polymerization because it suppresses the graft reaction with the following polymer, but it can be added and used after the graft reaction has sufficiently proceeded.

Examples of the polymerization initiator include normal radical polymerization initiators such as azobisisobutyronitrile and benzoyl peroxide.

The polymerization temperature is usually in the range of room temperature to 200 ° C, preferably 40 to 120 ° C. The polymerization concentration is usually 30 to 70% by weight, preferably
40-60% by weight.

The basic compound for forming the salt of the polysiloxane graft polymer can be used without limitation as long as it is conventionally used for the purpose of neutralizing an acidic substance, for example,
Sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine, methyldiethylamine, dimethylethylamine, monomethyloldimethylamine, monomethyloldiethylamine, dimethylolmethylamine, dimethylolethylamine and the like can be mentioned. One kind or two or more kinds can be used. The basic compound is used for making the polysiloxane graft polymer water-dispersible and for increasing the heat resistance, and the basic group of 20 to 20% of the acid group of the polymer is used.
Preference is given to using amounts corresponding to 200 mol%. 20
If the amount is less than mol%, a sufficient aqueous dispersion may not be obtained. In particular, in order to obtain a surface-modified composition which retains a good dispersion state even during storage and has no drawbacks such as a decrease in water resistance and discoloration caused by a basic compound, It is preferably added in an amount corresponding to 50 to 100 mol% of the acid groups of. At this time, when a high degree of dispersion stability is required, an appropriate emulsifier and / or protective colloid can be used in combination.

The amount of water added is 100% polysiloxane graft polymer.
It is 30 to 1000 parts by weight with respect to parts by weight. If it is less than 30 parts by weight, water does not form a continuous phase and a stable aqueous dispersion cannot be obtained. On the other hand, if the amount is more than 1000 parts by weight, the polysiloxane graft polymer is diluted and it is not economically preferable.

In order to stir the liquid containing the polysiloxane graft polymer to form a stable aqueous dispersion, the amount of the water-soluble organic solvent in the liquid is preferably 30 to 100% by weight based on the total amount of the organic solvent. Is. If the amount of the water-soluble organic solvent is less than 30% by weight, sedimentation of dispersed particles may occur and a sufficient aqueous dispersion may not be obtained. The proportion of the water-soluble organic solvent may be 30 to 100% by weight based on the whole organic solvent before or after the addition of water, but preferably before the addition.

Water-soluble organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, cyclic ethers such as tetrahydrofuran and dioxane, ketones such as acetone, and water-dilutable organics such as cellosolves such as methyl cellosolve and ethyl cellosolve. It is a solvent.

Considering the residual of the organic solvent preferably used for the polymerization, the ratio of the water-soluble organic solvent is preferably 40 to 90% by weight based on the whole organic solvent.

The aqueous dispersion of the salt of the basic compound of the polysiloxane graft polymer thus obtained can be suitably used as it is as a surface-modifying composition, but if the environmental protection during use is taken into consideration, further solvent removal is required. Is preferred. Desolvation can be easily performed by a conventionally known method such as vacuum distillation or heat distillation. The amount of solvent removal should be appropriately determined as desired, but it is contained in the dispersion liquid in order to maximize the features of the present invention.
It is preferred to remove an amount equal to or greater than weight%.

In the present invention, the water-soluble resin is used to further enhance the film-forming property, wettability, adhesion and the like of the aqueous dispersion of the salt of the basic compound of the polysiloxane graft polymer, and any water-soluble resin may be used without limitation. For example, polyvinyl alcohol, water-soluble acrylic resin, water-soluble polyester resin, water-soluble polyamide, water-soluble polyurethane resin, polyethylene glycol, polyacrylamide,
Cellulose, gelatin, etc. can be mentioned, and one kind or a mixture of two or more kinds selected from these groups can be used. Among them, polyvinyl alcohol can obtain a surface-modified composition having particularly excellent wettability. It is preferable because it is possible.

When using a water-soluble resin, the amount used is 50 parts by weight or less, preferably 0.01 to 20 parts by weight, more preferably 100 parts by weight of the solid content of the aqueous dispersion of the salt of the basic compound of the polysiloxane graft polymer. Is in the range of 0.1 to 5 parts by weight. If the amount is more than 50 parts by weight, the water resistance of the surface-modified composition is deteriorated, which is not preferable.

An aqueous resin composition comprising an aqueous dispersion of a salt of a polysiloxane graft polymer with a basic compound and a water-soluble resin can be prepared by: 1. Alternatively, a method of stirring and mixing under heating.

2. A method in which a liquid compound obtained by adding a basic compound, water and a water-soluble resin to a solution of a polysiloxane graft polymer is stirred and mixed at room temperature or under heating.

It can also be preferably produced by any of the above methods.

Further, as the crosslinking agent used in combination with the aqueous resin composition, those which can react at a temperature as low as possible are preferable, for example, dimethylol urea and other polymethylol urea, dimethylol ethylene urea, dimethylol glyoxal monourein, dimethylol glyoxal. Diurein, dimethylolurone, dimethylolpropyleneurea, 1,3-bis (hydroxymethyl) -tetrahydro-5-hydroxy-2-pyrimidinone, dimethyloltriazone, dimethylolmelamine and other polymethylolmelamine, polymethylolacetoguanamine , Polymethylol benzoguanamine and other polymethylol compounds; glyoxal, glutaraldehyde, dialdehyde starch and other polyaldehyde compounds; 1,6-hexamethylene diethylene urea, 1,1,1-tri (w-azide Gini propionate)
Polyaziridine compounds such as methylpropane; Nonionic water-soluble epoxy compounds such as diglycidyl ether of polyethylene glycol, glycerin diglycidyl ether, trimethylolpropane diglycidyl ether; Water-soluble glycidyl ester of acrylic acid or methacrylic acid and acrylamide Copolymer; polyamide epoxy resin; boric acid, borate; Na ₂ ZrSiO ₄ , ZrOCa ・ 3H ₂ O, ZrO
_{SO 4 · nH 2 O, ZrO} (NO 3) 2 · 4H 2 O, ZrO (CO 3) 2 · nH 2 O, Zr
O (OH) ₂・ nH ₂ O, ZrO (C ₂ H ₂ O ₂ ) ₂ , (NH ₄ ) ₂ ZrO (C
A zirconium compound represented by a chemical formula such as O ₃ ) ₂ or ZrSiO ₄ can be used. If necessary, a suitable curing acceleration catalyst may be used. The amount of the crosslinking agent used is preferably in the range of 1 to 30 parts by weight per 100 parts by weight of the aqueous resin composition (solid content conversion).

The aqueous dispersion of the salt of the basic compound of the polysiloxane graft polymer obtained as described above is excellent in long-term storage stability and is also excellent in water repellency, slipperiness, heat resistance, peeling property, anti-maglation property, etc. It can form a film and can be suitably used as it is as a surface-modifying composition, but if necessary, other known pigments, toners, lubricants, plasticizers, rust preventives, antistatic agents, etc. , A defoaming agent, a viscosity adjusting agent, a wetting agent, a PH adjusting agent and the like can be added. Further, it can be appropriately diluted.

〔The invention's effect〕

The surface-modified composition of the present invention has excellent long-term storage stability, and a coating film obtained by applying the same to a substrate has good adhesion to the substrate, and good water repellency and slipperiness. Resistance, heat resistance,
It exhibits excellent surface properties such as peelability and migration resistance, and is used for magnetic tape, back coating agents such as thermal printing materials, fiber treatment materials such as water repellent materials, adhesive tape, release paper,
It is applied to a release agent for heat-sensitive stencil sheet and the like, and exhibits excellent properties.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
All parts in the examples are parts by weight.

Reference Example 1 In a four-necked flask equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing tube and a stirrer, 30 weight parts of a linear dihydroxydimethylpolysiloxane having an average molecular weight of 120,000 as a terminal hydroxyl group-containing polysiloxane. % Toluene solution 10 parts and toluene 100 parts were charged, and a
The temperature was raised to 0 ° C. 20% by weight of a uniform monomer solution consisting of 70 parts of methyl methacrylate, 20 parts of butyl acrylate, 5 parts of acrylic acid, 5 parts of γ-methacryloxypropyltrimethoxysilane and 2 parts of azobisisobutyronitrile.
Was added to carry out initial polymerization at 80 ° C. for 30 minutes. Then, the remaining monomer homogeneous solution was added dropwise at the same temperature over 2 hours, and when the polymerization was continued for 2 hours and 30 minutes after the completion of the addition, 10 parts of isopropyl alcohol was added for dilution. Subsequently, while maintaining the temperature at 80 ° C., stirring was continued for 1 hour and 30 minutes to continue the polymerization reaction, followed by cooling to obtain a polysiloxane graft polymer solution (hereinafter, referred to as polymer solution (1)). To 40 parts of the obtained polymer solution (1), 60 parts of isopropyl alcohol was added to dilute, 3 parts of 28% ammonia water was added with stirring, and stirring was continued for 10 minutes, and then 237 parts of water was added. It was dispersed in water. Subsequently, the internal temperature was raised to 60 ° C, 250 parts were distilled off by vacuum distillation to remove the solvent, and then ammonia water and water were added to adjust the pH to 9.0 and the concentration to 30%. An aqueous polymer dispersion (hereinafter referred to as an aqueous dispersion (1)) was obtained. The obtained aqueous dispersion (1) has a viscosity of 10 cp
s (25 ℃, B type viscometer, 60 rpm)
It was a stable emulsion that did not cause sedimentation of dispersed particles and separation of polysiloxane. The residual isopropyl alcohol and toluene were 90 ppm and 750 ppm, respectively.

In order to check the storage stability of the liquid, when it was stored at 50 ° C. for 6 months, the polymer solution (1) was gelled, but the aqueous dispersion (1) was stable without change in viscosity.

Reference Example 2 A four-necked flask similar to that used in Reference Example 1 was prepared using Reference Example 1
33.3 parts of a 30 wt% toluene solution of a terminal hydroxyl group-containing polysiloxane similar to that used in
A part was charged and the temperature was raised to 80 ° C. under a nitrogen atmosphere. A uniform monomer solution consisting of 50 parts of methyl methacrylate, 20 parts of butyl acrylate, 20 parts of acrylonitrile, 5 parts of acrylic acid, 5 parts of γ-methacryloxypropyltrimethoxysilane and 2 parts of azobisisobutyronitrile was added thereto. Using the same, the same initial polymerization operation and dropping operation of the monomer homogeneous solution as in Reference Example 1 were performed. When the polymerization was continued for 30 minutes after the addition of the monomer uniform solution was completed, 100 parts of ethyl alcohol was added to dilute it. Further, the polymerization reaction is continued at 80 ° C. for 3 hours and 30 minutes and then cooled to obtain a solution of polysiloxane graft polymer (hereinafter,
It is called a polymer solution (2). ) Got. The same operation as in Reference Example 1 was performed except that 200 parts of the obtained polymer solution (2) was changed to 2.5 parts of 28% ammonia water, and the polysiloxane graft polymer aqueous dispersion (hereinafter referred to as the aqueous dispersion (2)). )
Got

The obtained aqueous dispersion (2) was a stable emulsion which did not cause sedimentation of dispersed particles or separation of polysiloxane even when allowed to stand for one week at a viscosity of 70 cps (25 ° C., B-type viscometer, 60 rpm). . The residual ethyl alcohol and toluene were 230 ppm and 870 ppm, respectively.

Reference Example 3 A four-necked flask similar to that used in Reference Example 1 had a terminal hydroxyl group-containing polysiloxane and an average molecular weight of 48.
3 parts of 000 linear dihydroxydimethylpolysiloxane and 100 parts of toluene were charged, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. 30 parts of methyl methacrylate, 30 parts of styrene
Part, vinyl acetate 25 parts, acrylic acid 10 parts, 2-styrylethyltrimethoxysilane 5 parts and azobisisobutyronitrile 2 parts using a homogeneous solution of a monomer, the same initial polymerization operation as in Reference Example 1 And the dropping operation of the monomer homogeneous solution was performed. When the polymerization was continued for 15 minutes after the addition of the monomer uniform solution was completed, 100 parts of isopropyl alcohol was added for dilution. Further, the polymerization reaction was continued at 80 ° C. for 3 hours and 45 minutes and then cooled to obtain a polysiloxane graft polymer solution (hereinafter referred to as a polymer solution (3)). To 200 parts of the obtained polymer solution (3), 2 parts of 28% mammonia water was added with stirring, the stirring was continued for 10 minutes, and then 238 parts of water was added,
Water dispersion was performed to obtain a polysiloxane graft polymer aqueous dispersion (hereinafter, referred to as an aqueous dispersion (3)).

The obtained aqueous dispersion (3) has a viscosity of 750 cps (25 ° C., B-type viscometer, 60 rpm), and is a stable emulsion that does not cause sedimentation of dispersed particles or separation of polysiloxane even when allowed to stand for one week. It was

Reference Example 4 A polysiloxane graft polymer aqueous dispersion was prepared in the same manner as in Reference Example 2 except that the amount of acrylonitrile in Reference Example 2 was changed from 20 parts to 5 parts and the amount of acrylic acid was changed from 5 parts to 20 parts. (Hereinafter, referred to as an aqueous dispersion (4)). The obtained aqueous dispersion (4) has a viscosity of 220 cps (25 ° C, B
-Type viscometer, 60 rpm), it was a stable emulsion that did not cause sedimentation of dispersed particles or separation of polysiloxane even after standing still for 1 week, and the residual ethyl alcohol and toluene were 300 ppm and 1100 ppm, respectively. .

Reference Example 5 Instead of the polysiloxane containing a terminal hydroxyl group used in Reference Example 1, a 30 wt% toluene solution of a partially branched branched dimethylpolysiloxane having an average of 4 terminal hydroxyl groups and an average molecular weight of 260,000. The same operation as in Reference Example 1 was carried out except that was used to obtain a polysiloxane graft polymer aqueous dispersion (hereinafter referred to as an aqueous dispersion (5)). The obtained aqueous dispersion (5) has a viscosity of 12 cps (25 ° C, B
It was a stable emulsion that did not cause sedimentation of dispersed particles or separation of polysiloxane even when it was allowed to stand for one week using a viscometer (60 rpm). The residual isopropyl alcohol and toluene were 70 ppm and 800 ppm, respectively.

Comparative Reference Example 1 A polymer solution for comparison (hereinafter, referred to as polymer solution for comparison (1)) was prepared in the same manner as in Reference Example 1 except that γ-methacryloxypropyltrimethoxysilane in Reference Example 1 was not used. ) Got. To 140 parts of the obtained comparative polymer solution (1) was added 60 parts of isopropyl alcohol to dilute, 3 parts of 28% ammonia water was added with stirring, and stirring was continued for 10 minutes, and then 237 parts of water was added. Then, it was dispersed in water to obtain a comparative aqueous dispersion (hereinafter referred to as comparative aqueous dispersion (1)). When the obtained comparative aqueous dispersion (1) was allowed to stand overnight, polysiloxane separated into an upper layer.

Comparative Reference Example 2 302 parts of a polymer solution obtained in exactly the same manner as in Reference Example 1 except that the terminal hydroxyl group-containing polysiloxane in Reference Example 1 was not used, had the same terminal hydroxyl groups as those used in Reference Example 1. 10 parts of a group-containing polysiloxane as a 30 wt% toluene solution was added and mixed well to obtain a comparative polymer solution (hereinafter referred to as a comparative polymer solution (2)). To 140 parts of the obtained comparative polymer solution (2) was added 60 parts of isopropyl alcohol, and after dilution, 3 parts of 28% ammonia water was added with stirring, and after stirring for 10 minutes, water was added.
237 parts was added and dispersed in water to obtain a comparative aqueous dispersion (hereinafter referred to as comparative aqueous dispersion (2)). When the obtained comparative aqueous dispersion (2) was allowed to stand overnight, polysiloxane separated into an upper layer.

Comparative Reference Example 3 The same operation as in Reference Example 1 was carried out except that the amount of acrylic acid in Reference Example 1 was changed from 5 parts to 0.5 part, and a polysiloxane graft polymer aqueous dispersion for comparison (hereinafter referred to as an aqueous dispersion for comparison) was prepared. (3).) Was obtained. When the obtained comparative aqueous dispersion (3) was allowed to stand for one week, particles settled and a transparent aqueous layer portion was separated in the upper layer.

Comparative Reference Example 4 The same four-necked flask as used in Reference Example 1 was charged with 220 parts of deionized water and 1 part of an anionic emulsifier and heated to 80 ° C. under a nitrogen atmosphere. On the other hand, 3 parts of polysiloxane macromer in which the molecular weight of the dimethylsiloxane part is 10,000 and the terminal is methacryloxypropyl group and methyl group, 70 parts of methyl methacrylate, 20 parts of butyl acrylate, 5 parts of acrylic acid.
Part, γ-methacryloxypropyltrimethoxysilane 5
A uniform solution of the monomer was prepared. 10% by weight of this homogeneous solution of monomer and 10% of ammonium persulfate
While adding 10 parts of the aqueous solution to the above four-necked flask,
The temperature was raised to 0 and the initial emulsion polymerization was performed for 10 minutes. After the initial emulsion polymerization was completed, the remaining monomer homogeneous solution was added dropwise at the same temperature over 2 hours, and then stirring was continued for 2 hours while maintaining the temperature at 80 ° C to continue the polymerization reaction and emulsify. The polymerization reaction was completed. When the comparative polysiloxane graft polymer aqueous dispersion thus obtained (hereinafter referred to as comparative aqueous dispersion (4)) was allowed to stand, the polysiloxane component was separated in the upper layer and a uniform aqueous dispersion could not be obtained. .

Examples 1 to 8, Comparative Examples 1 to 4 and Conventional Example 1 Aqueous dispersions (1) to (5) obtained in Reference Examples 1 to 5 and comparative aqueous dispersions (1) obtained in Comparative Reference Examples 1 to 4 ) To (4) and the polymer solution (1), the water-soluble resin and the cross-linking agent of the types and amounts shown in Table 1 were added to 100 parts of each solid content, and the mixture was added at room temperature for 15
The surface-modifying composition (1) to (8) of the present invention, which is stirred for a minute.
Comparative surface modifying compositions (1) to (4) and conventional compositions were prepared.

The performance of these compositions was evaluated by the performance test method shown below. The evaluation results are shown in Table 1. Regarding the slipperiness and water repellency, the measured values of the glass plate are also shown for reference.

1) Sliding property: A surface-modifying composition having a thickness of 1.5 μm was coated on a glass plate, dried at 100 ° C. for 1 minute, and allowed to stand overnight. A test piece was used to measure the dynamic friction coefficient of a coating film. Therefore, the slipperiness was evaluated. The dynamic friction coefficient was measured using a surface property measuring instrument (HEIDON-14 type manufactured by Shinto Scientific Co., Ltd.).

2) Water repellency: The same test piece as in the slip test was used.
Water repellency was evaluated by measuring the contact angle of the coating film to water. The contact angle was measured by a droplet method using a contact angle measuring device (CA-A type manufactured by Kyowa Interface Science Co., Ltd.).

3) Heat resistance: A surface-modifying composition is applied to one side of a polyester film having a thickness of 6 μ to a thickness of 1.5 μ, dried at 100 ° C. for 1 minute, and left overnight, and a heat-meltable ink is applied to the other side. Applied. The coated surface of the surface modification composition was placed on the thermal head side and overlapped with the image receiving paper, and a thermal transfer test was performed on the recording paper using a thermal head printing test device (manufactured by Matsushita Electronic Parts Co., Ltd.). The test conditions are as follows: applied voltage is 20V, printing speed is 2
It was a millisecond. The heat resistance was evaluated by observing the running state of the film for the presence or absence of the heat stick phenomenon during the heat transfer test.

4) Peelability and migration resistance: A surface-modifying composition having a thickness of 15 μm was applied to high-quality paper, dried at 130 ° C. for 10 minutes, and allowed to stand at room temperature for 2 hours. Nichiban polyester tape) was crimped. After this was stored at 35 ° C. for 1 week, the adhesive tape was peeled off from the high-quality paper, and the peeling force was measured to evaluate the peeling property. Further, the peeled pressure-sensitive adhesive tape was pressure-bonded to a stainless steel plate, and the residual adhesive strength of the pressure-sensitive adhesive tape was measured to evaluate migration resistance. The peeling force and residual adhesive force are
Expressed by the peeling force by 180 degree peeling test, the peeling speed is 30 cm /
Went in minutes.

The migration resistance of the surface-modified composition can be evaluated based on the magnitude of the residual adhesive strength. When the residual adhesive force is large, delamination of the coating film is unlikely to occur and the migration resistance is good. In addition, when the residual adhesive strength is small, delamination of the coating film (especially, the polysiloxane component in the coating film is removed) easily occurs, and the migration resistance is poor.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C10M 107/50 9159-4H

Claims (6)

[Claims] 1. A polymerizable silane compound (B) in an amount of 1 to 20% by weight in the presence of a terminal hydroxyl group-containing polysiloxane (A) in an amount of 0.05 to 10% by weight, an unsaturated organic acid (C) in an amount of 1 to 30% by weight, and these Other polymerizable monomer (D) copolymerizable with
Polymer obtained by polymerizing 40 to 97.95% by weight (however, the total of the components (A), (B), (C) and (D) is 100% by weight) in an organic solvent other than alcohol. 100 parts by weight of an aqueous dispersion of a salt of a basic compound of a polysiloxane graft polymer and a water-soluble resin obtained by stirring a liquid material obtained by adding a basic compound and water to the solution of the aqueous dispersion (solid content (Conversion) per 0 to 5 of the water-soluble resin
A surface-modifying composition comprising 0 part by weight. 2. A polysiloxane graft polymer aqueous dispersion, wherein the amount of the basic compound added is 20 to 200 mol% of the acid groups in the polysiloxane graft polymer, and the amount of water added is 100 parts by weight of the polysiloxane graft polymer. The amount of the water-soluble organic solvent in the liquid material before or after the addition of water is 30 to 100 parts by weight with respect to the total amount of the organic solvent. The surface-modified composition according to claim 1, which is a composition. 3. An aqueous dispersion of a salt of a basic compound of a polysiloxane graft polymer, which is obtained by dispersing an aqueous dispersion of a salt of a basic compound of a polysiloxane graft polymer in water and then removing the solvent. Alternatively, the surface modification composition according to claim 2. 4. The surface modification composition according to claim 1, which further comprises a crosslinking agent. 5. The water-soluble resin is 0.01 with respect to 100 parts by weight (in terms of solid content) of the polysiloxane graft polymer aqueous dispersion.
The surface modification composition according to any one of claims 1 to 4, having a proportion of -20 parts by weight. 6. The surface modification composition according to claim 1, wherein the water-soluble resin is polyvinyl alcohol.