JPH05209149A - Coating composition - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of an aqueous emulsion of a specific polysiloxane-polyvinyl graft copolymer, free from toxicity, having excellent smoothness, water and oil repellency, mold-releasability and re-staining resistance and useful for the coating of a thermoplastic resin film, etc. CONSTITUTION:The objective composition is composed of an emulsion of a polysiloxane-polyvinyl graft copolymer composed mainly of (A) one or more kinds of siloxane units selected from the siloxane units of formula I and formula II [R<1> and R<2> are (substituted) hydrocarbon group; A<1> is bivalent organic group; B<1> is vinyl monomer block or vinyl polymer block] and (B) one or more kinds of siloxane units selected from the siloxane units of the formula SiO2, formula III and formula IV [R<1> is (substituted) hydrocarbon group; A<2> is bivalent organic group; B<2> is B<1>]. The molar ratio of A/B is 99/1 to 0/100 and the sum of the siloxane unit of formula II and/or the siloxane unit of formula IV is >=0.5mol% based on the total siloxane unit.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to coating compositions.
Carrier materials such as magnetic recording media, packaging materials, electrical / electronic-related materials, plate-making materials, printing materials, photographic film materials, thermal transfer recording media, and thermoplastic resin films used for heat-sensitive stencil sheets, etc. It is required to have surface properties such as oiliness, releasability and stain resistance. The present invention relates to an aqueous emulsion type coating composition suitable for meeting the above requirements, and particularly suitable for imparting the above-mentioned surface characteristics to a thermoplastic resin film used for a thermal transfer recording medium or a heat-sensitive stencil sheet. ..

[0002]

2. Description of the Related Art Conventionally, as means for imparting the above-mentioned surface characteristics to a carrier material, 1) a means for applying a composition containing a polymerizable monomer and irradiating it with radiation, plasma, etc.,
2) Means for applying a coupling agent such as an oligomer or silane, 3) Means for applying a composition obtained by adding a silicone-based graft copolymer to an organic solvent type paint (JP-A-58-1).
54766, JP-A-58-164656), 4) Means for applying a composition obtained by adding a fluorine-based graft copolymer or a silicone-based graft copolymer to an emulsion type coating (JP-A-60-243167). ..

However, the conventional means of 1) requires a) a special device and is uneconomical, while the conventional means of 2) has b) inferior surface properties imparted thereto and the conventional method of 3). The means are c) highly toxic and inferior in imparted surface characteristics,
The conventional means of 4) has a disadvantage that d) the applied composition is inhomogeneous and thus the surface properties imparted are inferior.

[0004]

The problems to be solved by the present invention are a) to d) in the conventional means of 1) to 4).
Is a drawback.

[0005]

However, the present inventors have
As a result of intensive studies to solve the above problems, it was found that a coating composition comprising an aqueous emulsion of a graft copolymer having a specific structure in which a vinyl monomer is grafted or graft-polymerized on a polyorganosiloxane is properly suitable. It was

That is, the present invention shows one or more kinds of siloxane units (A) selected from the siloxane unit represented by the following formula 1 and the siloxane unit represented by the following formula 2, and the following formula 3. A siloxane unit (A), a siloxane unit represented by the following formula 4, and one or more siloxane units (B) selected from the siloxane units represented by the following formula 5 as main constituent units. / Siloxane unit (B) = 99/1 to 0/10
Polysiloxane-polyvinyl graft containing the siloxane unit represented by the formula 2 and / or the siloxane unit represented by the formula 5 in an amount of 0 (molar ratio) as a total amount of 0.5 mol% or more of all siloxane units. A coating composition comprising an aqueous emulsion of a copolymer.

[0007]

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[In the formulas 1 to 5, R ^{1 to} R ³ are hydrocarbon groups having a carbon atom directly bonded to a silicon atom, which are the same or different at the same time, and which are unsubstituted or have no radical polymerizable property. A ¹ : having a carbon atom directly bonded to a silicon atom and B ¹
A divalent organic group linked to. A ² : having a carbon atom directly bonded to a silicon atom and B ²
A divalent organic group linked to. B ^1, B ^2: vinyl monomer block or a vinyl polymer block. ]

In the present invention, the polysiloxane-polyvinyl graft copolymer is a polysiloxane containing a siloxane unit represented by the formula 2 and / or a siloxane unit represented by the formula 5, each having a vinyl monomer block or a vinyl polymer block. It is an organosiloxane. In such a polysiloxane-polyvinyl graft copolymer, one having both the siloxane unit (A) and the siloxane unit (B) as main constituent units, and one having only the siloxane unit (B) as main constituent unit Is included.

The polysiloxane-polyvinyl graft copolymer having both siloxane units (A) and siloxane units (B) as main constituent units is used in a total amount of 100 mol% of siloxane units (A) and siloxane units (B). The content of the siloxane unit (A) is 99 mol% or less, and the content of the siloxane unit (B) is 1 mol% or more. The siloxane unit (A) / the siloxane unit (B) = 99/1 to 80/2.
Those which are contained at a ratio of 0 (molar ratio) are preferable. The polysiloxane-polyvinyl graft copolymer having both the siloxane unit (A) and the siloxane unit (B) as main constitutional units is a total amount of the siloxane unit represented by the formula 2 and / or the siloxane unit represented by the formula 5. Is 0.5 mol% or more of all the siloxane units, and the polysiloxane-polyvinyl graft copolymer having only the siloxane unit (B) as a main constituent unit has the siloxane unit represented by the formula 5 as 0% of all the siloxane units. It contains 0.5 mol% or more.

In the formulas 1, 2 and 4, R ^{1 to} R ³ are unsubstituted or substituted hydrocarbon groups having a carbon atom directly bonded to a silicon atom and having no radical polymerizable property. Among these, examples of the unsubstituted hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an aralkyl group, and the like. Among them, a methyl group, an ethyl group, a butyl group and the like having 1 to 10 carbon atoms. An alkyl group of 4 or a phenyl group is advantageously selected. Further, examples of the substituted hydrocarbon group include a substituted hydrocarbon group having a halogen, an epoxy group, a cyano group, a ureido group or the like as a substituent, and among them, a γ-glycidoxypropyl group and β-
(3,4-Epoxy) cyclohexylethyl group, γ-chloropropyl group, trifluoropropyl group and the like are advantageously selected. These unsubstituted hydrocarbon group and substituted hydrocarbon group can be in any ratio.

In formulas 2 and 5, A ¹ and A ² have a carbon atom directly bonded to a silicon atom, and A ¹ is B
¹ and A ² are divalent organic groups linked to B ² . A ¹
And A ² are important as groups for connecting the vinyl monomer block or vinyl polymer block to the polyorganosiloxane. Examples of A ¹ and A ² include ethylene group, propylene group, 3-oxo-4-oxa-1,7-heptanediyl group, 2-methyl-3-oxo-4-oxa-1,
Examples thereof include 7-heptanediyl group and trimethylenethioxy group.

In the formulas 2 and 5, B ¹ and B ² are vinyl monomer blocks obtained by grafting vinyl monomers or vinyl polymers obtained by graft polymerization or copolymerization of vinyl monomers. It is a block. A vinyl monomer block obtained by grafting a vinyl monomer having no fluorine substituent or a vinyl monomer having no fluorine substituent is graft-polymerized or graft-copolymerized on B ¹ and B ^2. In addition to the vinyl polymer block obtained, a vinyl monomer block obtained by grafting a vinyl monomer having a fluorine substituent or a vinyl monomer containing a vinyl monomer having a fluorine substituent is graft-polymerized. Alternatively, a vinyl polymer block obtained by graft copolymerization is included. The vinyl polymer block obtained by graft-polymerizing or graft-copolymerizing a vinyl monomer containing a vinyl monomer having a fluorine substituent is graft-polymerized with a vinyl monomer having a fluorine substituent. Alternatively, in addition to the vinyl polymer block obtained by graft copolymerization, a vinyl polymer block obtained by graft copolymerizing a vinyl monomer having a fluorine substituent and a vinyl monomer not having a fluorine substituent is obtained. (Hereinafter, these are simply referred to as vinyl monomer blocks or vinyl polymer blocks).

As the vinyl monomer having no fluorine substituent, 1) alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and cyclohexyl methacrylate,
2) Alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, 3) Aromatic vinyl monomers such as styrene and α-methylstyrene, 4)
Vinyl esters such as vinyl benzoate, vinyl acetate, etc. 5) Sodium styrenesulfonate, sodium allylsulfonate, sodium vinylsulfonate, methacryloyloxyethyltrimethylammonium chloride, acrylic acid, vinyl monomer having an ionic group such as methacrylic acid Body, 6) water-soluble vinyl monomers such as acrylamide, polyethylene glycol methacrylate and hydroxyethyl methacrylate, 7) vinyl monomers having a reactive group such as glycidyl methacrylate and maleic anhydride, and the like. Aromatic vinyl monomer,
Those containing 90% by weight or more of one or more selected from alkyl (meth) acrylate and acrylonitrile, particularly styrene, methyl (meth) acrylate and ethyl (meth) acrylate are preferable.

As the vinyl monomer having a fluorine substituent, 1) 1H, 1H, 11H-eicosafluoroundecyl acrylate, 1H, 1H-heptafluorobutyl acrylate, hexafluoroisopropyl acrylate, 1H, 1H. , 5H-octafluoropentyl acrylate, 1H, 1H-pentadecafluorooctyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,2-trifluoroethyl acrylate and other fluoroalkyl acrylates,
2) 1H, 1H, 11H-eicosafluoroundecyl methacrylate, 1H, 1H-heptafluorobutyl methacrylate, hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H-pentadecafluorooctyl methacrylate , 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,2-trifluoroethyl methacrylate and other fluoroalkyl methacrylates, 3) 2, 2,3,3-tetrafluoropropyl-2- (trifluoromethyl) propenoate, 2,
Α-Fluoroalkylacrylic acid esters such as 2,2-trifluoroethyl-2- (trifluoromethyl) propenoate, 4) α-fluoroalkylvinylcarboxylic acid esters such as 1- (trifluoromethyl) vinyl acetate, 5) Fluorocarboxylic acid vinyl esters such as vinyl trifluoroacetate; 6) Fluoro-substituted styrenes such as 3-fluorostyrene and 4-fluorostyrene; 7) α- such as α-trifluoromethylstyrene.
Examples thereof include fluoroalkyl styrenes and the like, and among them, those having no fluorine substituent or fluoroalkyl group in the vicinity of the vinyl group are preferable. This is because the electron absorption of fluorine and the steric effect of the fluoroalkyl group are less affected and the graft polymerizability or graft copolymerizability is excellent. When using a vinyl monomer having no fluorine substituent and a vinyl monomer having a fluorine substituent as the vinyl monomer, each has a fluorine substituent, an aromatic vinyl monomer, vinyl carboxylate, Those containing 2% by weight or more of one or more selected from alkyl (meth) acrylates are preferable.

In the present invention, the polysiloxane-polyvinyl graft copolymer has both the siloxane unit (A) and the siloxane unit (B) as main constituent units as described above, or only the siloxane unit (B). However, the present invention does not particularly limit the kind of the terminal group which is a constitutional unit other than the main constitutional unit in the polysiloxane-polyvinyl graft copolymer. Examples of such an end group include hydrogen, a hydroxyl group,
Examples thereof include a trimethylsilyl group, and among them, a trimethylsilyl group is preferable.

Next, a method for producing an aqueous emulsion of polysiloxane-polyvinyl graft copolymer in the present invention will be described. First, a compound capable of forming a silanol group by hydrolysis (hereinafter referred to as a silanol group-forming compound) is hydrolyzed in an aqueous medium in the presence of a hydrolysis catalyst such as an acid or an alkali to produce a silanol compound. Next, the silanol compound is polycondensed in the presence of a polycondensation catalyst such as an inorganic acid or an organic acid to form an aqueous emulsion of polyorganosiloxane. In order to make the average particle size of the aqueous emulsion smaller to produce a more stable aqueous emulsion, it is necessary to appropriately use a surfactant in the hydrolysis reaction system of the silanol group-forming compound or the condensation polymerization reaction system of the silanol compound. it can. Finally, a vinyl monomer and a radical polymerization catalyst are added to an aqueous emulsion of polyorganosiloxane to carry out grafting or graft polymerization or graft copolymerization to introduce a vinyl monomer block or a vinyl polymer block into the polyorganosiloxane. An aqueous emulsion of the desired polysiloxane-polyvinyl graft copolymer is thus obtained.

In the above manufacturing method, examples of the silanol group-forming compound include various alkoxysilanes, chlorosilanes, hydrogensilanes, acyloxysilanes, cyclosiloxane compounds and the like. In the present invention, a silanol group-forming compound such that 2 to 4 silanol groups are formed by hydrolysis is mainly used,
For the purpose of adjusting the polycondensation degree of the silanol compound having a silanol group formed and introducing a terminal group, a silanol group-forming compound such that one silanol group is formed by hydrolysis is used as a total silanol group-forming compound. It can be used in the range of 4 mol% or less based on the compound. Further, in the present invention, in order to introduce a vinyl monomer block or a vinyl polymer block into the polyorganosiloxane as described above, as a silanol group-forming compound, a functional group such as a radically polymerizable group or a thiol group is contained in the molecule. A silanol group-forming compound having a group is used. The ratio of the silanol group-forming compound having such a functional group is 7.5 mol% or less based on all the silanol group-forming compounds.

Examples of the silanol group-forming compound capable of forming four silanol groups include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane and tetrachlorosilane. Examples of silanol group-forming compounds capable of forming three silanol groups include methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, phenyltrimethoxysilane, methyltris (dimethylamino) silane, methyltrichlorosilane, and phenyl. Examples thereof include trichlorosilane, methyldichloromethoxysilane, methyldichlorohydrogensilane, methylsilanetriol, methyldichlorosilanol, and methylchlorosilanediol.

Examples of the silanol group-forming compound capable of forming two silanol groups include 1) silane compounds such as dimethyldimethoxysilane, dimethyldichlorosilane, dimethyldihydrogensilane, and dimethylchlorosilanol, and 2) octamethylcyclo. Examples include cyclosiloxane compounds such as tetrasiloxane. Further, as a silanol group-forming compound capable of forming one silanol group,
1) silane compounds such as trimethylmethoxysilane, trimethylchlorosilane, trimethylhydrogensilane, and 2) siloxane compounds such as hexamethyldisiloxane.

As the silanol group-forming compound having a functional group, 1) three silanol groups such as methacryloyloxypropyl trimethoxysilane, vinyl trimethoxysilane, aryl trimethoxysilane, and mercaptopropyl trimethoxysilane. 2) a silane having two silanol groups such as methacryloyloxypropyl methyl dimethoxysilane, vinyl methyl dimethoxysilane, aryl methyl dimethoxysilane, and mercaptopropyl methyl dimethoxysilane. Compound, 3) 1 silanol such as methacryloyloxypropyl dimethyl methoxysilane, vinyl dimethyl methoxysilane, aryl dimethyl methoxysilane, mercaptopropyl dimethyl methoxysilane, etc. Silane compound groups are formed and the like.

As the silanol group-forming compound, a silanol group-forming compound having a hydrocarbon group substituted with a polar group such as a glycidyl group, an ureido group or an amino group can be used in any proportion. When the silanol group-forming compound having such a substituted hydrocarbon group is used in the range of 5 to 30 mol% with respect to the total silanol group-forming compounds, the average particle size of the obtained aqueous emulsion is further reduced and its stability is improved. It is preferable for further improving. As the silanol group-forming compound having a substituted hydrocarbon group,
1) γ-glycidoxypropyl trimethoxysilane,
γ-ureidopropyl trimethoxysilane, N, N-
A silane compound in which three silanol groups are formed, such as dimethylaminopropyl trimethoxysilane, 2) γ-glycidoxypropyl methyldimethoxysilane, γ-
Ureidopropyl methyl dimethoxysilane, N, N
A silane compound in which two silanol groups such as dimethylaminopropyl / methyl / dimethoxysilane are formed,
3) A silane compound in which one silanol group is formed, such as γ-glycidoxypropyl dimethyl methoxysilane, γ-ureidopropyl dimethyl methoxy silane, and N, N-dimethylaminopropyl dimethyl methoxy silane. Can be mentioned.

In order to produce an aqueous emulsion of the polysiloxane-polyvinyl graft copolymer in the present invention, the silanol group-forming compound is hydrolyzed in an aqueous medium and the silanol compound thus produced is polycondensed as described above. To obtain an aqueous emulsion of polyorganosiloxane, the aqueous medium used here is 30% by weight or more of water,
It is preferably a homogeneous solvent containing 90% by weight or more. Examples of the solvent that can be used in combination with water include water-soluble solvents such as methanol, ethanol, isopropanol, acetone and tetrahydrofuran.

Grafting or graft polymerization or graft copolymerization in which a vinyl monomer block or a vinyl polymer block is introduced into a polyorganosiloxane is carried out by adding a radical polymerization catalyst and a vinyl monomer to an aqueous emulsion of polyorganosiloxane. It is performed by stirring under an active gas atmosphere. The reaction at this time can be carried out in the temperature range of room temperature to the boiling point of the vinyl monomer used. In the case of grafting or graft polymerization or graft copolymerization, when the vinyl monomer is bound through the radically polymerizable carbon-carbon double bond or thiol group contained in the polyorganosiloxane, its relative amount used. According to the above, an aqueous emulsion of a polysiloxane-polyvinyl graft copolymer in which the vinyl monomer is grafted, graft-polymerized or graft-copolymerized is obtained.

In the present invention, the ratio of polyorganosiloxane moiety / grafted vinyl monomer moiety or graft-polymerized or graft-copolymerized vinyl polymer moiety is 99/1 to 22/78 (weight) from the viewpoint of physical properties. ratio)
Is preferred. Further, in order to exhibit superior performance to a coating composition comprising an aqueous emulsion of polysiloxane-polyvinyl graft copolymer, the particles contained in the aqueous emulsion have an average particle diameter of 0.01.
To 0.5 μm are preferable, and 0.02 to 0.3 μm
Are more preferred.

The concentration of the polysiloxane-polyvinyl graft copolymer contained in the aqueous emulsion is not limited, but a concentration of 5 to 50% by weight is advantageous in terms of production and stability. When the aqueous emulsion is specifically used as a coating composition, the aqueous emulsion is diluted with water so as to have an appropriate concentration, and various films or sheets are formed by a known method such as a roller touch method or a spray method. Etc. to a carrier material.

As a carrier material to which the coating composition of the present invention is applied, a thermoplastic resin film or sheet selected from polyester, nylon and polypropylene is preferable, and a polyester film or sheet is particularly preferable. In this case, surface properties such as smoothness, water / oil repellency, anti-adhesion properties, releasability, and stain resistance can be imparted to the polyester film or sheet to a higher degree. When the coating composition of the present invention is applied to the thermoplastic resin film or sheet as described above, the concentration of the polysiloxane-polyvinyl graft copolymer contained in the coating composition is an aqueous emulsion. Usually 0.1-10
After diluting with water so as to be 1% by weight, preferably 1 to 5% by weight, it is applied by a known method such as a roller touch method or a spray method. The step of applying is a step of producing a thermoplastic resin film or sheet, a step before stretch orientation immediately after melt extrusion, a step before biaxial stretch orientation after uniaxial stretch orientation, or a step after biaxial stretch orientation. Although it may be any of the above, the step before the biaxially stretched orientation after the uniaxially stretched orientation is preferable, and when applied in any step, it is usually a film of a thermoplastic resin which is a product as a polysiloxane-polyvinyl graft copolymer or The amount of coating is 0.01 to 0.2 g per 1 m ^{2 of the} sheet.

[0028]

【Example】

-Test Category 1 The following aqueous emulsions were prepared, and the average particle size and dispersion stability of the aqueous emulsions are summarized in Table 1. The average particle size and the dispersion stability are measured or evaluated as follows.

Average particle diameter: The aqueous emulsion prepared in each example was measured by a dynamic light scattering method using an electrophoretic light scattering photometer (ELS-800, manufactured by Otsuka Electronics Co., Ltd.).

Dispersion stability: The aqueous emulsion prepared in each example was placed in a glass container which was tightly closed and allowed to stand, and the presence or absence of a sedimentation layer at the bottom of the container and the presence or absence of a supernatant layer at the top of the container, It was observed and evaluated according to the following criteria. ×: Sedimentation layer or supernatant layer was observed after standing for 1 day Δ: Sedimentation layer or supernatant layer was observed between 2 days and 1 week ○: 1 week later to 1 month A sedimented layer or a supernatant layer was observed ◎: A sedimented layer or a supernatant layer was not observed even after 1 month

Example 1 1080 g of ion-exchanged water was charged into a reaction vessel, and acetic acid of 0.
2 g was added to make a uniform solution. 1333 g (9.78 mol) of methyltrimethoxysilane and 27 g (0.11 g) of γ-methacryloxypropyltrimethoxysilane.
Mol) and 394 g (1.67 mol) of γ-glycidoxypropyltrimethoxysilane, and the hydrolysis reaction was carried out while maintaining the temperature at 30 ° C. A transparent reaction solution containing a silanol compound was obtained in about 30 minutes. Next, 475 g of ion-exchanged water and 50 g of dodecylbenzene sulfonic acid were placed in another reaction vessel, dissolved well, and the temperature was adjusted to 80-8.
The temperature was 5 ° C. To this, 300 g of the reaction solution obtained above was added dropwise over about 2 hours. After aging for 15 minutes, the mixture was gradually cooled and stirred for 1 hour until it reached room temperature. After completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium carbonate solution to obtain a non-linear polyorganosiloxane aqueous emulsion. The fine particles of the non-linear polyorganosiloxane contained in this aqueous emulsion had an average particle diameter of 0.08 μm. To the aqueous emulsion obtained above, 1 g of potassium persulfate and 163 g of ion-exchanged water were added, and the temperature was adjusted to 70 under a nitrogen gas atmosphere.
The temperature was adjusted to ˜75 ° C., and 47.2 g of styrene was added dropwise over about 1 hour. After the dropping was completed, the temperature was maintained for about 3 hours to complete the polymerization. The polysiloxane-polyvinyl graft copolymer in the obtained aqueous emulsion is spherical solid particles, the average particle diameter of which is 0.09 μm, the solid content concentration of the aqueous emulsion is 20%, and the polysiloxane in the aqueous emulsion is -The concentration of polyvinyl graft copolymer is 1
It was 5.2%.

Example 2 100 g of octamethylcyclotetrasiloxane (0.3 g
4 mol) with sodium dodecylbenzenesulfonate 1
g was added to 300 g of dissolved ion-exchanged water, preliminarily stirred at 10000 rpm with a homomixer, and then passed through a homogenizer at a pressure of 350 kg / cm ² three times for emulsification and dispersion. To this, 780 g of ion-exchanged water was added, 0.2 g of formic acid was added and mixed, and the mixture was stirred at 20 ° C. for 30 minutes. While stirring this at 20 ° C., 1200 g (8.8 mol) of methyltrimethoxysilane, 27 g (0.11 mol) of γ-methacryloxypropyltrimethoxysilane and 120 of γ-glycidoxypropyltrimethoxysilane.
g (0.51 mol) was added, and hydrolysis was performed while maintaining the temperature at 30 ° C. A reaction solution containing a silanol compound was obtained in about 30 minutes. Next, 475 g of ion-exchanged water and 32.6 g of lauryldimethylhydroxyethylammonium hydroxide were placed in another reaction vessel, dissolved well, and then the temperature was adjusted to 80 to 85 ° C. To this, 300 g of the reaction solution obtained above was added dropwise over about 2 hours. After aging for 15 minutes, the mixture was gradually cooled and stirred for 1 hour until it reached room temperature. After completion of the reaction, adjust to pH 7.0 with a weak hydrochloric acid aqueous solution,
An aqueous emulsion of non-linear polyorganosiloxane was obtained. The non-linear polyorganosiloxane fine particles contained in this aqueous emulsion had a mean particle size of 0.10 μm. To this aqueous emulsion, 1 g of potassium persulfate and 1725 g of ion-exchanged water were added, and the temperature was adjusted to 70 to 75 ° C. under a nitrogen gas atmosphere.
A mixed monomer of 32 g and 57 g of methyl acrylate was added dropwise over about 1 hour. After the dropping was completed, the temperature was maintained for about 3 hours to complete the polymerization. The polysiloxane-polyvinyl graft copolymer in the obtained aqueous emulsion was spherical solid particles having an average particle diameter of 0.14 μm.
m, the solid content concentration of the aqueous emulsion was 20%, and the concentration of the polysiloxane-polyvinyl graft copolymer in the aqueous emulsion was 18.8%.

Example 3 394 g of γ-glycidoxypropyltrimethoxysilane in Example 1 was added to 191 g (0.81 mol) of γ-glycidoxypropyltrimethoxysilane and 187 g (0.90 mol) of tetraethyl silicate. The same operation as in Example 1 was performed except that it was replaced. The polysiloxane-polyvinyl graft copolymer in the obtained aqueous emulsion was substantially spherical, the average particle diameter was 0.05 μm, the solid content concentration of the aqueous emulsion was 20%, and the polysiloxane-polyvinyl in the aqueous emulsion was 20%. The concentration of the graft copolymer was 15.2%.

Example 4 Same as Example 1 except that 27 g of γ-methacryloxypropyltrimethoxysilane in Example 1 was replaced with 34.8 g (0.15 mol) of γ-methacryloxypropylmethyldimethoxysilane. The operation was performed. The polysiloxane-polyvinyl graft copolymer in the obtained aqueous emulsion was spherical solid particles and had an average particle diameter of 0.0
8 μm, the solid content concentration of the aqueous emulsion was 20%, and the concentration of the polysiloxane-polyvinyl graft copolymer in the aqueous emulsion was 16.3%.

Example 5 1333 g of methyltrimethoxysilane in Example 1
And γ-glycidoxypropyltrimethoxysilane 394
g to methyltrimethoxysilane 1648 g (12.1 mol), γ-methacryloxypropyltrimethoxysilane from 27 g to 36 g (0.15 mol), dodecylbenzenesulfonic acid from 50 g to 80 g,
The same operation as in Example 1 was performed except that the amount of styrene was changed from 47.2 g to 62.5 g. The polysiloxane-polyvinyl graft copolymer in the obtained aqueous emulsion was spherical solid particles having an average particle diameter of 0.20 μm.
The solid content concentration of the aqueous emulsion was 24%, and the concentration of the polysiloxane-polyvinyl graft copolymer in the aqueous emulsion was 16.6%.

Example 6 Octamethylcyclotetrasiloxane 97.7 g (0.
33 mol), γ-glycidoxypropyltrimethoxysilane 4.6 g (19.6 mmol) and γ-methacryloxypropyltrimethoxysilane 2.0 g (8.1 mmol) were mixed, and this was mixed with dodecylbenzenesulfonic acid. 1.
After adding 0 g to 300 g of ion-exchanged water in which it was dissolved, the mixture was dispersed with a homomixer and then homogenized with a homogenizer to obtain an aqueous emulsion of silanol compound. Next, 31 g of dodecylbenzene sulfonic acid and 217 g of ion-exchanged water were charged into the flask and well dissolved, then the temperature was adjusted to 80
The temperature was raised to ˜85 ° C., and the aqueous emulsion of the silanol compound obtained above was added dropwise thereto over 2 hours. After completion of dropping, the mixture was aged at 85 ° C. for 1 hour. After completion of the aging, the mixture was cooled to room temperature and neutralized with sodium carbonate to complete polycondensation to obtain an aqueous polyorganosiloxane emulsion. Finally, 483 g of ion-exchanged water and 1.5 g of potassium persulfate were dissolved in the aqueous polyorganosiloxane emulsion obtained above, which was transferred to a flask and heated to 70 ° C. while flowing nitrogen into the flask. 100 g was slowly added dropwise. After completion of dropping, the mixture was aged for 3 hours to obtain an aqueous emulsion of polysiloxane-polyvinyl graft copolymer. The average particle size of the polysiloxane-polyvinyl graft copolymer contained in the aqueous emulsion is 0.0
6 μm, the solid content concentration of the aqueous emulsion is 19.1.
%, The concentration of polysiloxane-polyvinyl graft copolymer in the aqueous emulsion was 16.3%.

Example 7 Octamethylcyclotetrasiloxane 100.6 g
(0.34 mol), hexamethyldisiloxane 1.6 g
(0.01 mol) and 3.3 g (13.3 mmol) of γ-methacryloxypropyltrimethoxysilane are mixed,
This was added to 315 g of ion-exchanged water in which 1.1 g of dodecylbenzenesulfonic acid was dissolved, dispersed with a homomixer, and then uniformly emulsified with a homogenizer to obtain 421 g of an aqueous emulsion of silanol compound. Next, an aqueous emulsion of silanol compound was charged into a flask,
After polycondensation at 5 ° C. for 5 hours, the mixture was gradually cooled for 16 hours, neutralized with a saturated aqueous solution containing 0.32 g of sodium carbonate, and filtered to obtain an aqueous emulsion of polyorganosiloxane. Finally, the aqueous polyorganosiloxane emulsion obtained above was charged into a flask, and potassium persulfate 1.6 was added.
g and 400 g of ion-exchanged water were added and the mixture was heated to 70 ° C.
After replacing the inside of the flask with nitrogen, 45 g (0.43 mol) of styrene was added dropwise over 2 hours. After completion of dropping, the mixture was heated to 80 ° C. and aged for 4 hours. Slowly cool to 40 ° C, filter,
An aqueous emulsion of polysiloxane-polyvinyl graft copolymer was obtained. The polysiloxane-polyvinyl graft copolymer contained in the aqueous emulsion had an average particle diameter of 0.30 μm, and the solid content concentration of the aqueous emulsion was 1
6.9%, the concentration of polysiloxane-polyvinyl graft copolymer in the aqueous emulsion was 16.8%.

Example 8 204.2 g of octamethylcyclotetrasiloxane
(0.69 mol), γ-glycidoxypropyltrimethoxysilane 20.2 g (0.085 mol), γ-methacryloxypropyltrimethoxysilane 4.8 g (19.
3 mmol), and this was added to 750 g of ion-exchanged water in which 2.5 g of dodecylbenzenesulfonic acid was dissolved,
After dispersing with a homomixer, the mixture was homogenized with a homogenizer to obtain an aqueous emulsion of silanol compound. Then add dodecylbenzene sulfonic acid 77.
After charging 5 g and ion-exchanged water 542.5 g and dissolving well, the temperature was raised to 80 to 85 ° C., and the aqueous emulsion of the silanol compound obtained above was added dropwise thereto over 2 hours. After completion of dropping, the mixture was aged at 85 ° C. for 1 hour. After completion of the aging, the mixture was cooled to room temperature and neutralized with sodium carbonate to complete polycondensation to obtain an aqueous polyorganosiloxane emulsion. Finally, 725 g of ion-exchanged water and 2.3 g of potassium persulfate were dissolved in the aqueous polyorganosiloxane emulsion obtained above, transferred to a flask, and heated to 70 ° C. while flowing nitrogen into the flask, and 224.9 g (1.61 mol) of trifluoroacetate
Was slowly added dropwise. After completion of dropping, the mixture was aged for 3 hours to obtain an aqueous emulsion of polysiloxane-polyvinyl graft copolymer. The polysiloxane-polyvinyl graft copolymer contained in the aqueous emulsion had an average particle size of 0.26 μm, and the solid content concentration of the aqueous emulsion was 2 μm.
0.8%, the concentration of polysiloxane-polyvinyl graft copolymer in the aqueous emulsion was 17.5%.

Example 9 Octamethylcyclotetrasiloxane 97.7 g (0.
33 mol), 1.8 g of hexamethyldisiloxane (1
1.1 mmol), 6.4 g (25.8 mmol) of γ-methacryloxypropyltrimethoxysilane, and 2.8 g of dodecylbenzenesulfonic acid were dissolved in 234 g of deionized water, and treated in the same manner as in Example 8, An aqueous emulsion of polyorganosiloxane was obtained. The polyorganosiloxane aqueous emulsion obtained above, potassium persulfate 2.5 g, ion-exchanged water 967.5 g, methyl methacrylate 50.0 g and 4-fluorostyrene 2
Using 5.0 g, an aqueous emulsion of polysiloxane-polyvinyl graft copolymer was obtained in the same manner as in Example 8. The average particle size of the polysiloxane-polyvinyl graft copolymer contained in the aqueous emulsion was 0.
22 μm, the solid content concentration of the aqueous emulsion is 13.1
%, The concentration of polysiloxane-polyvinyl graft copolymer in the aqueous emulsion was 12.9%.

Comparative Example 1 A reaction vessel was charged with 288 g of ion-exchanged water, 50 g of dodecylbenzenesulfonic acid was added to form a uniform solution, and the temperature was raised to 60 ° C. A mixed solution of 170 g (1.25 mol) of methyltrimethoxysilane and 2.8 g (0.012 mol) of γ-glycidoxypropyltrimethoxysilane was added dropwise thereto over 3 hours. Stirring was continued for 12 hours at a temperature of 60 ° C. and neutralized with an aqueous sodium carbonate solution to obtain an aqueous emulsion of polyorganosiloxane. The polyorganosiloxane contained in the aqueous emulsion is spherical solid particles as a whole, and the average particle diameter thereof is 0.90 μm.
However, irregular-shaped particles and agglomerated particles were observed in addition to spherical particles, and the solid content concentration of the aqueous emulsion was 27.2.
%, The concentration of polyorganosiloxane in the aqueous emulsion was 16.8%.

Comparative Example 2 300 g of ion-exchanged water was charged into a reaction vessel, and 1 g of dodecylbenzenesulfonic acid was added to make a uniform solution. Octamethylcyclotetrasiloxane 98.9g
(0.35 mol) and γ-glycidoxypropylmethyldimethoxysilane (4.2 g, 0.019 mol) were added, and the mixture was predispersed with a rotary stirring blade and then made into an emulsion with a homogenizer. This emulsion was transferred to a reaction vessel, heated while stirring, and subjected to hydrolysis and polycondensation at a temperature of 80 to 85 ° C. for 7 hours, cooled to room temperature, neutralized with an aqueous sodium hydrogen carbonate solution, and then treated with polyorgano. An aqueous emulsion of siloxane was obtained. The average particle size of the polyorganosiloxane contained in the aqueous emulsion is 5 μm or more, and
Coarse particles of 00 μm or larger were observed, the solid content concentration of the aqueous emulsion was 25.5%, and the polyorganosiloxane concentration in the aqueous emulsion was 25.2%.

Comparative Example 3 100 g of polydimethylsiloxane having one end modified with a methacryloyloxypropyl group (average molecular weight: 5000)
Was dissolved in 500 g of xylene, charged into a flask with 0.2 g of azobisisobutylnitrile, and heated to 70 ° C. After replacing the inside of the flask with nitrogen, 100 g of methyl methacrylate was added dropwise over 2 hours. 80 after dropping
Aged at ℃ for 4 hours. After completion of aging, the mixture was gradually cooled, reprecipitated with excess methanol, and filtered. 100 g of the dried solid matter was added to 850 g of ion-exchanged water in which 50 g of sodium dodecylbenzenesulfonate was dissolved, and the mixture was emulsified with a homogenizer to obtain an aqueous emulsion.

Comparative Example 4 Linear polydimethylsiloxane (average molecular weight 1000
0) 15 g, sodium dodecylbenzene sulfonate 2
g was dissolved in 88 g of ion-exchanged water and emulsified with a homogenizer to obtain an aqueous emulsion.

Comparative Example 5 2000 g of ion-exchanged water was charged into a reaction vessel, and 4 g of dodecylbenzenesulfonic acid was added to make a uniform solution.
Octamethylcyclotetrasiloxane 395.6
g (1.4 mol) and γ-methacryloxypropyltrimethoxysilane 1.4 g (5.6 mmol),
After preliminarily dispersing with a rotary stirring blade, an emulsion was prepared with a homogenizer. This emulsion was transferred to a reaction vessel, heated while stirring, and subjected to hydrolysis and polycondensation at a temperature of 80 to 85 ° C. for 7 hours, cooled to room temperature, neutralized with an aqueous sodium hydrogen carbonate solution, and then treated with polyorgano. An aqueous emulsion of siloxane was obtained. 2 g of potassium persulfate was added to the aqueous polyorganosiloxane emulsion obtained above, stirred for 20 minutes, and styrene 1 was added at 65 to 70 ° C. while flowing nitrogen gas.
00g was added dropwise over 30 minutes and then at 65-70 ° C for 4
Hold for time to complete the polymerization. The average particle size of the polysiloxane-polyvinyl graft copolymer contained in the obtained aqueous emulsion was 5 μm or more, the solid content concentration of the aqueous emulsion was 20%, and the polysiloxane-polyvinyl graft copolymer of the aqueous emulsion contained The concentration is 19.
It was 9%.

[0045]

[Table 1]

Test Category 2 Polyethylene terephthalate having an intrinsic viscosity of 0.62 measured in orthochlorophenol at 25 ° C. and containing no inorganic filler was extruded from a die with an extruder and cooled to 40 ° C. While applying static electricity on the above, make an extruded film with a thickness of 152μ,
Then, in the longitudinal direction on a metal roll heated to 93 ° C.
It was stretched 6 times to obtain a uniaxially stretched film. Next, immediately before the uniaxially stretched film reached the tenter, one side of the uniaxially stretched film was uniformly coated with the aqueous emulsion prepared in Test Category 1 from a coater head consisting of three rolls. The coating amount at this time was about 2.3 g per 1 m ^{2 of the} above uniaxially stretched film (the coating amount corresponds to about 0.0129 g per 1 m ^{2 in the following} biaxially stretched film). Finally, the uniaxially stretched film coated on one side was introduced into a tenter, stretched 3.5 times in the transverse direction at 101 ° C., and further heat-fixed at 225 ° C. for 6.3 seconds to obtain a biaxially stretched film (one sided). After coating, the film was heated for a total of 11 seconds). The biaxially stretched film could be wound at a tension of 9.8 kg without generating wrinkles. Further, the biaxially stretched film was microslit to a width of 1/2 inch to produce 52 tapes of 500 mg, and during this period, microslitting could be favorably performed without any problems. Table 2 shows the coatability of the aqueous emulsion prepared in Test Category 1, the appearance of the biaxially stretched film, the water drop contact angle, the friction coefficient and the releasability. These are measured or evaluated as follows.

Coatability: When the aqueous emulsion is applied on one side of the uniaxially stretched film, the wet state of the aqueous emulsion and the uniformity of the coating film formed on the biaxially stretched film are visually observed, and the following criteria are used. evaluated. ◯: No spots are observed at all Δ: Slight spots are observed ×: Remarkably spots are observed

Appearance of the film: The transparency of the biaxially stretched film was visually observed and evaluated according to the following criteria. ◯: The entire surface has the same transparency as that of the untreated film. Δ: The part with inferior transparency is recognized in 1 part. ×: The entire surface is opaque.

Water drop contact angle: 23 ° C. on a biaxially stretched film
Water drops were dropped under an atmosphere of 65% RH, and the contact angle was measured with a goniometer (manufactured by Institute of Industrial Science, University of Tokyo).

Friction coefficient: Biaxially stretched film at 23 ° C. × 6
Humidity was controlled in an atmosphere of 5% RH, and the friction coefficient (μd) for the stainless steel plate on the satin surface was measured under the same conditions as the friction coefficient measuring machine (TR type manufactured by Toyo Seiki Co., load 200 g, speed 300 mm).
/ Min).

Releasability: An adhesive tape was attached to the coating surface of the biaxially stretched film, cut into a width of 20 mm, and the 180 ° peeling force was measured by a tensile tester.

[0052]

[Table 2]

[0053]

As is apparent from the above, according to the present invention described above, a carrier material such as a thermoplastic resin film does not require a special device, is economical, has no toxicity, and has a high degree of efficiency. There is an effect that surface characteristics such as smoothness, water / oil repellency, releasability and stain resistance can be imparted.

Claims (6)

[Claims] 1. A 1 selected from a siloxane unit represented by the following formula 1 and a siloxane unit represented by the following formula 2.
One or more siloxane units (A) and the following formula 3
A siloxane unit represented by the following formula 4, a siloxane unit represented by the following formula 4 and a siloxane unit (B) represented by the following formula 5: A) / siloxane unit (B) = 99/1 to 0/100 (molar ratio), and the total amount of the siloxane unit represented by formula 2 and / or the siloxane unit represented by formula 5 is the total amount. A coating composition comprising an aqueous emulsion of a polysiloxane-polyvinyl graft copolymer containing 0.5 mol% or more of siloxane units. [Formula 1] [Formula 2] [Formula 3] [Formula 4] [Formula 5] [In Formulas 1 to 5, R ^{1 to} R ³ are hydrocarbon groups having a carbon atom directly bonded to a silicon atom, and at the same time, the same or different, unsubstituted or substituted hydrocarbon radicals having no radical polymerizability. A ¹ : having a carbon atom directly bonded to a silicon atom and B ¹
A divalent organic group linked to. A ² : having a carbon atom directly bonded to a silicon atom and B ²
A divalent organic group linked to. B ^1, B ^2: vinyl monomer block or a vinyl polymer block. ] B ² of 2. A formula 2 in B ¹ and Formula 5 is a vinyl monomer containing one or more vinyl monomers selected from aromatic vinyl monomers and alkyl (meth) acrylate The coating composition according to claim 1, which is a vinyl polymer block obtained by graft polymerization of a polymer. B ² of 3. Formula 2 B ¹ and Equation 5, respectively having a fluorinated substituent, the aromatic vinyl monomer, vinyl carboxylate and alkyl (meth) one or more selected from acrylate The coating composition according to claim 1, which is a vinyl polymer block obtained by graft-polymerizing the vinyl monomer containing 2% by weight or more of the vinyl monomer. 4. The siloxane unit (A) and the siloxane unit (B) are contained at a ratio of siloxane unit (A) / siloxane unit (B) = 99/1 to 80/20 (molar ratio). The coating composition according to 2 or 3. 5. The particles of the polysiloxane-polyvinyl graft copolymer contained in the aqueous emulsion have an average particle diameter of 0.01 to 0.5 μm.
The coating composition described. 6. The coating composition according to claim 1, which is applied to a film or sheet of a thermoplastic resin selected from polyester, nylon and polypropylene.