JP3192247B2 - Processing method of polyethylene terephthalate film or polyethylene terephthalate sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for treating a polyethylene terephthalate film or a polyethylene terephthalate sheet. Magnetic recording media, packaging materials, electrical and electronic related materials, plate making materials, printing materials, photographic film materials,
A polyethylene terephthalate film or a polyethylene terephthalate sheet used for a thermal transfer recording medium, a heat-sensitive stencil sheet or the like is required to have surface properties such as smoothness, water and oil repellency, mold release properties, and stain resistance. . The present invention relates to a method for treating a polyethylene terephthalate film or a polyethylene terephthalate sheet, which satisfies such demands, in particular, can provide the above-mentioned surface characteristics to a polyethylene terephthalate film used for a thermal transfer recording medium or a heat-sensitive stencil sheet.

[0002]

2. Description of the Related Art Conventionally, as a method for imparting the above-mentioned surface characteristics to a polyethylene terephthalate film or a polyethylene terephthalate sheet, 1) a composition containing a polymerizable monomer is applied, and the composition is irradiated with radiation, plasma or the like. Method 2) A method of applying a coupling agent such as an oligomer or silane, and 3) A method of applying a composition obtained by adding a silicone-based graft copolymer to an organic solvent type paint (JP-A-58-154766; 58-164656),
4) Fluorine-based graft copolymer in emulsion type paint
A method of applying a composition to which a silicone-based graft copolymer has been added (Japanese Patent Application Laid-Open No. 60-243167).

However, the conventional method of 1) requires a) special equipment and is uneconomical, and the conventional method of 2) has b) inferior surface characteristics imparted to the conventional method of 3). In the law,
The c) is highly toxic and has poor surface properties imparted. The conventional method 4) has the disadvantage that d) the surface properties imparted are poor because the composition to be applied is heterogeneous.

[0004]

The problem to be solved by the present invention is the disadvantages a) to d) in the conventional methods 1) to 4).

[0005]

Means for Solving the Problems Thus, the present inventors have
As a result of intensive studies to solve the above-mentioned problems, an aqueous emulsion of a graft copolymer having a specific structure obtained by grafting or graft-polymerizing a vinyl monomer to a polyorganosiloxane, wherein the graft copolymer contained in the aqueous emulsion is contained. It has been found that it is correct and suitable to apply an aqueous emulsion having an average particle diameter of the coalesced particles in a predetermined range to a polyethylene terephthalate film or a polyethylene terephthalate sheet before or after stretch orientation.

That is, the present invention relates to an aqueous emulsion of a graft copolymer represented by the following formula 1, wherein the average particle diameter of the graft copolymer particles is 0.01 to 0.5 μm.
m, wherein the aqueous emulsion is applied to a polyethylene terephthalate film or a polyethylene terephthalate sheet.

[0007]

(Equation 1)

[Where R ^{1 to} R ³ are a hydrocarbon group having a carbon atom directly bonded to a silicon atom and having the same or different, unsubstituted or substituted, non-radical polymerizable property. A: having a carbon atom directly bonded to a silicon atom, and B
A divalent organic group linked to B: Vinyl monomer block or vinyl polymer block. T ¹ , T ² : a silyl terminal group represented by the following formula 2 or 3.

(Equation 2)

(Equation 3) (R ⁴ ~R ^8: same .Y as for ^{R 1 ~R 3: A-B} , H or OH.) A: 50 to 4000 integer. b: Integer satisfying 1 ≦ b ≦ a / 20. The siloxane unit formed by a and the siloxane unit formed by b are bonded in a block or random manner. ]

In the formula 1, R ^{1 to} R ³ (the same applies to R ^{4 to} R ⁸ ) are an unsubstituted or substituted, non-radical polymerizable hydrocarbon group having a carbon atom directly bonded to a silicon atom. is there. 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. Four alkyl groups or phenyl groups are advantageously chosen. As the substituted hydrocarbon group, a halogen atom, an epoxy group,
Substituted hydrocarbon groups having a cyano group, a ureido group and the like, among which γ-glycidoxypropyl group, β-
(3,4-Epoxy) cyclohexylethyl, γ-chloropropyl, trifluoropropyl and the like are advantageously selected. These unsubstituted hydrocarbon groups and substituted hydrocarbon groups can be in any ratio.

In the formula 1, A is a divalent organic group having a carbon atom directly bonded to a silicon atom and being bonded to B. A is important as a group connecting a vinyl monomer block or a vinyl polymer block to the polyorganosiloxane. Examples of A include an ethylene group, a propylene group, a 3-oxo-4-oxa-1,7-heptanediyl group, a 2-methyl-3-oxo-4-oxa-1,7-heptanediyl group, and a trimethylenethioxy group. And the like.

In the formula 1, B is a vinyl monomer block obtained by grafting a vinyl monomer or a vinyl polymer block obtained by graft polymerization or graft copolymerization of a vinyl monomer. Such B is a vinyl monomer block obtained by grafting a vinyl monomer having no fluorine substituent or a vinyl polymer obtained by graft polymerization or graft copolymerization of a vinyl monomer having no fluorine substituent. In addition to the coalesced block, graft polymerization or graft copolymerization of 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 And a vinyl polymer block obtained by the above method.
Here, a vinyl monomer having a fluorine substituent is graft-polymerized onto a vinyl polymer block obtained by graft polymerization or graft copolymerization of a vinyl monomer containing a vinyl monomer having a fluorine substituent. Or, 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 having no fluorine substituent is included (hereinafter, these are simply referred to as a vinyl monomer block or a vinyl monomer block). Polymer block).

Examples of the vinyl monomer having no fluorine substituent include: 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-methyl styrene; 4)
Vinyl esters such as vinyl benzoate and vinyl acetate; 5) vinyl monomer having an ionic group such as sodium styrenesulfonate, sodium allylsulfonate, sodium vinylsulfonate, methacryloyloxyethyltrimethylammonium chloride, acrylic acid and methacrylic acid; And 6) a water-soluble vinyl monomer such as acrylamide, polyethylene glycol methacrylate, and hydroxyethyl methacrylate; and 7) a vinyl monomer having a reactive group such as glycidyl methacrylate and maleic anhydride. Aromatic vinyl monomer,
Those containing at least 90% by weight of one or more selected from alkyl (meth) acrylate and acrylonitrile, particularly styrene, methyl (meth) acrylate and ethyl (meth) acrylate are preferred.

The above-mentioned vinyl monomers having a fluorine substituent include: 1) 1H, 1H, 11H-eicosafluoroundecyl acrylate, 1H, 1H-heptafluorobutyl acrylate, hexafluoroisopropyl acrylate, 1H, 1H Fluoroalkyl acrylates such as 1,5H-octafluoropentyl acrylate, 1H, 1H-pentadecafluorooctyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,2-trifluoroethyl acrylate;
2) 1H, 1H, 11H-eicosafluoroundecyl methacrylate, 1H, 1H-heptafluorobutyl methacrylate, hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H-pentadecafluorooctyl methacrylate Fluoroalkyl methacrylates such as 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate and 2,2,2-trifluoroethyl methacrylate; 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) vinyl fluorocarboxylates such as vinyl trifluoroacetate; 6) fluoro-substituted styrenes such as 3-fluorostyrene and 4-fluorostyrene; 7) α- such as α-trifluoromethylstyrene.
Examples thereof include fluoroalkylstyrenes, among which those having no fluorine substituent or fluoroalkyl group near the vinyl group are preferable. This is because the effect of the electron absorption of fluorine and the steric effect due to the fluoroalkyl group is small, and the graft copolymerizability 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 having 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 preferred.

In the formula (1), T ¹ , T ² , a and b are silyl end groups as described in the proviso of the formula (1) or an integer in a predetermined range.

Next, a method for producing the aqueous emulsion of the graft copolymer used in the present invention will be described. First, a compound capable of forming a silanol group by hydrolysis (hereinafter, referred to as a compound)
A silanol group-forming compound) 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 reduce the average particle diameter of the aqueous emulsion to produce a more stable aqueous emulsion, a surfactant is appropriately used in a hydrolysis reaction system of the silanol group-forming compound or a polycondensation reaction system of the silanol compound. it can. Finally, a vinyl monomer and a radical polymerization catalyst are added to the aqueous emulsion of the polyorganosiloxane to perform grafting, graft polymerization or graft copolymerization, thereby introducing a vinyl monomer block or a vinyl polymer block into the polyorganosiloxane. Thus, an aqueous emulsion of the desired graft copolymer is obtained.

In the above-mentioned production 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 in which two silanol groups are formed by hydrolysis is mainly used, but for the purpose of adjusting the degree of polycondensation of the silanol compound having two silanol groups formed. A silanol group-forming compound that forms one silanol group by hydrolysis can be used in an amount of 4 mol% or less based on all silanol group-forming compounds. Further, in the present invention, as described above, in order to introduce a vinyl monomer block or a vinyl polymer block into the polyorganosiloxane, a silanol group-forming compound, such as a radical polymerizable group or a thiol group, is used 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 set to 7.5 mol% or less based on all the silanol group-forming compounds.

Examples of the silanol group-forming compound in which two silanol groups are formed include: 1) a silane compound such as dimethyldimethoxysilane, dimethyldichlorosilane, dimethyldihydrogensilane and dimethylchlorosilanol; and 2) octamethylcyclo. Cyclosiloxane compounds such as tetrasiloxane are exemplified. Examples of the silanol group-forming compound in which one silanol group is formed include:
1) Silane compounds such as trimethylmethoxysilane, trimethylchlorosilane and trimethylhydrogensilane; and 2) siloxane compounds such as hexamethyldisiloxane. Further, as a silanol group-forming compound having a functional group, 1) two compounds such as methacryloyloxypropyl methyl dimethoxysilane, vinyl methyl dimethoxysilane, aryl methyl dimethoxysilane, and mercaptopropyl methyl dimethoxysilane; A silane compound in which a silanol group is formed, 2) methacryloyloxypropyl dimethyl methoxy silane,
Vinyl dimethyl methoxysilane, aryl dimethyl methoxysilane, mercaptopropyl dimethyl
A silane compound in which one silanol group is formed, such as methoxysilane.

As the silanol group-forming compound, a silanol group-forming compound having a hydrocarbon group substituted by a polar group such as a glycidyl group, a ureide group or an amino group can be used at an arbitrary ratio. 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 compound, the average particle diameter of the obtained aqueous emulsion is reduced, and the stability thereof is improved. It is preferable in order to further improve. As the silanol group-forming compound having a substituted hydrocarbon group,
1) a silane compound in which two silanol groups are formed, such as γ-glycidoxypropyl methyl dimethoxysilane, γ-ureidopropyl methyl dimethoxysilane, N, N-dimethylaminopropyl methyl dimethoxysilane, 2) A silane compound in which one silanol group is formed, such as γ-glycidoxypropyl dimethyl methoxy silane, γ-ureidopropyl dimethyl methoxy silane, and N, N-dimethylaminopropyl dimethyl methoxy silane No.

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

In the grafting, graft polymerization or graft copolymerization in which a vinyl monomer block or a vinyl polymer block is introduced into a polyorganosiloxane, a radical polymerization catalyst and a vinyl monomer are added to an aqueous emulsion of a polyorganosiloxane. This is performed by stirring under an active gas atmosphere. The reaction at this time can be carried out in a temperature range from room temperature to the boiling point of the vinyl monomer used. In the case of grafting, graft polymerization or graft copolymerization, when a vinyl monomer is bonded via a radically polymerizable carbon-carbon double bond contained in the polyorganosiloxane, An aqueous emulsion of a graft copolymer obtained by grafting or graft-polymerizing or graft-copolymerizing the vinyl monomer is obtained, and the vinyl monomer is bonded via a thiol group contained in the polyorganosiloxane. Gives an aqueous emulsion of a graft copolymer grafted with the vinyl monomer.

In the aqueous emulsion used in the present invention, the ratio of the polyorganosiloxane moiety / grafted vinyl monomer moiety or the graft polymerized or graft copolymerized vinyl polymer moiety in the graft copolymer contained in the aqueous emulsion is as follows: 9 from the viewpoint of physical properties
It is preferably 9/1 to 22/78 (weight ratio). Further, in the aqueous emulsion used in the present invention, the graft copolymer contained in the aqueous emulsion has an average particle diameter of the particles is in the range of 0.01 to 0.5 μm, preferably 0.02 to 0.3 μm In the range of When the average particle diameter is less than 0.01 μm, or conversely, exceeds 0.5 μm, an aqueous emulsion of the graft copolymer having such an average particle diameter is applied to a polyethylene terephthalate film or a polyethylene terephthalate sheet. However, these materials cannot be provided with the desired surface properties.

The concentration of the graft copolymer contained in the aqueous emulsion is not limited, but a concentration of 5 to 50% by weight is advantageous from the viewpoint of production and stability. When such an aqueous emulsion is applied to a polyethylene terephthalate film or a polyethylene terephthalate sheet, the concentration of the graft copolymer contained in the aqueous emulsion is usually 0.1 to 10% by weight, preferably 1 to 10% by weight.
After diluting with water so as to have a concentration of about 5% by weight, coating is performed by a known method such as a roller touch method or a spray method. The step of applying the aqueous emulsion is, in the process of producing a polyethylene terephthalate film or a polyethylene terephthalate sheet, a step before stretch orientation immediately after melt extrusion, a step before biaxial stretch orientation after uniaxial stretch orientation, or biaxial stretch orientation. Any of the following steps may be performed, but a step before biaxial stretching orientation after uniaxial stretching orientation is preferable, and even when applying in any step, usually,
It applied so as to product a polyethylene terephthalate film or product polyethylene terephthalate sheet 1 m ² per 0.01~0.2g as a graft copolymer.

[0023]

EXAMPLES Test Category 1 Aqueous emulsions of the following examples were produced, and the average particle size and dispersion stability of the aqueous emulsions are shown in Table 1. The average particle size and 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 produced in each example was placed in a sealed glass container and allowed to stand, and the presence or absence of a settling layer at the bottom of the container and the presence of a supernatant layer at the top of the container were determined. Observation was evaluated according to the following criteria. ×; a sedimentary layer or a supernatant layer was observed after standing for one day Δ: a sedimentation layer or a supernatant layer was observed between two days and one week ○: between one week and one month A sedimentation layer or a supernatant layer was observed. ◎: A sedimentation layer or a supernatant layer was not observed even after one month.

Production Example 1 Octamethylcyclotetrasiloxane 100.6 g
(0.34 mol), 1.6 g of hexamethyldisiloxane
(0.01 mol), 2.0 g (8.8 mmol) of γ-methacryloxypropylmethyldimethoxysilane, 1.1 g of dodecylbenzenesulfonic acid, and 315 g of ion-exchanged water
And homogenized with a homogenizer to obtain 421 g of an aqueous emulsion of a silanol compound. Next, an aqueous emulsion of a silanol compound was charged into a flask, polycondensed at 80 ° C. for 5 hours, and then gradually cooled for 16 hours to obtain sodium carbonate 0.32.
Neutralized with a saturated aqueous solution containing g and filtered to obtain an aqueous emulsion of polyorganosiloxane. Finally, the aqueous emulsion of polyorganosiloxane obtained above was charged into a flask, and 1.6 g of potassium persulfate and 40 g of ion-exchanged water were added.
0 g was added and heated to 70 ° C. After the atmosphere in the flask was replaced with nitrogen, 45 g (0.43 mol) of styrene was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was heated to 80 ° C. and aged for 4 hours. The mixture was gradually cooled to 40 ° C. and filtered to obtain an aqueous emulsion of the graft copolymer.

..Production Example 2 156.9 g of octamethylcyclotetrasiloxane
(0.53 mol), 2.7 g of hexamethyldisiloxane
(16.8 mmol), γ-methacryloxypropylmethyldimethoxysilane 3.1 g (13.5 mmol),
1.7 g of dodecylbenzenesulfonic acid was added to deionized water 4
The resultant was dissolved in 90 g, and an aqueous emulsion of polyorganosiloxane was obtained in the same manner as in Production Example 1. And the aqueous emulsion of polyorganosiloxane obtained above,
An aqueous emulsion of a graft copolymer was obtained in the same manner as in Production Example 1, using 0.53 g of potassium persulfate, 245 g of ion-exchanged water, and 18.2 g (0.18 mol) of methyl methacrylate.

Production Example 3 Octamethylcyclotetrasiloxane 162.8 g
(0.55 mol), 3.3 g (13.3 mmol) of γ-methacryloxypropyltrimethoxysilane, and 2.8 g of dodecylbenzenesulfonic acid in ion-exchanged water 2
The resultant was dissolved in 34 g, and an aqueous emulsion of polyorganosiloxane was obtained in the same manner as in Production Example 1. And the aqueous emulsion of polyorganosiloxane obtained above,
2.5 g of potassium persulfate, 967.5 g of ion-exchanged water,
An aqueous emulsion of a graft copolymer was obtained in the same manner as in Production Example 1 using 82.5 g (0.83 mol) of methyl methacrylate and 82.5 g (0.49 mol) of cyclohexyl methacrylate.

Production Example 4 100.6 g of octamethylcyclotetrasiloxane
(0.34 mol), 1.6 g of hexamethyldisiloxane
(0.01 mol), 2.0 g (8.8 mmol) of γ-methacryloxypropylmethyldimethoxysilane, 1.1 g of dodecylbenzenesulfonic acid, and 315 g of ion-exchanged water
And an aqueous emulsion of polyorganosiloxane was obtained in the same manner as in Production Example 1. Then, the aqueous emulsion of polyorganosiloxane obtained above, 1.6 g of potassium persulfate, 735 g of ion-exchanged water, and styrene 5
2.5 g (0.5 mol), 52.5 g of acrylonitrile
(0.99 mol), and an aqueous emulsion of a graft copolymer was obtained in the same manner as in Production Example 1.

Production Example 5 97.7 g of octamethylcyclotetrasiloxane (0.
33 mol), 4.6 g (19.6 mmol) of γ-glycidoxypropyltrimethoxysilane and 2.0 g (8.1 mmol) of γ-methacryloxypropyltrimethoxysilane were mixed, and this was mixed with dodecylbenzenesulfonic acid. 1.
0 g was added to 300 g of dissolved ion-exchanged water, and the mixture was dispersed with a homomixer and then uniformly emulsified with a homogenizer to obtain an aqueous emulsion of a silanol compound. Next, 31 g of dodecylbenzenesulfonic acid and 217 g of ion-exchanged water were charged into the flask and dissolved well.
The temperature was raised to ８５85 ° C., and an aqueous emulsion of a silanol compound was added dropwise thereto over 2 hours. After dropping, 85 ° C
For 1 hour. After completion of the aging, the mixture was cooled to room temperature and neutralized with sodium carbonate to complete the polycondensation to obtain an aqueous emulsion of polyorganosiloxane. Finally, 483 g of ion-exchanged water and 1.5 g of potassium persulfate were dissolved in the aqueous emulsion of polyorganosiloxane obtained above and transferred to a flask. 100 g (0.96 mol)
Was slowly added dropwise. After completion of the dropwise addition, the mixture was aged for 3 hours to obtain an aqueous emulsion of the graft copolymer.

Production Example 6 An aqueous emulsion of the polyorganosiloxane obtained in Production Example 1 was charged into a flask, 1.6 g of potassium persulfate and 400 g of ion-exchanged water were added, and the mixture was heated to 70.degree. After the atmosphere in the flask was replaced with nitrogen, 45 g (0.20 mol) of hexafluoroisopropyl acrylate was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was heated to 80 ° C. and aged for 4 hours. 4
The mixture was gradually cooled to 0 ° C. and filtered to obtain an aqueous emulsion of the graft copolymer.

Production Example 7 204.2 g of octamethylcyclotetrasiloxane
(0.69 mol), 20.0 g (0.091 mol) of γ-glycidoxypropylmethyldimethoxysilane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane
(20.8 mmol), and 750 g of ion-exchanged water in which 2.5 g of dodecylbenzenesulfonic acid was dissolved.
In addition, the mixture was dispersed with a homomixer, and then uniformly emulsified with a homogenizer to obtain an aqueous emulsion of a silanol compound. Next, 77.5 g of dodecylbenzenesulfonic acid and 542.5 g of ion-exchanged water were charged into the flask, and after well dissolving, the temperature was raised to 80 to 85 ° C., and an aqueous emulsion of a silanol compound was added dropwise over 2 hours. did. After completion of the dropwise addition, 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 the polycondensation to obtain an aqueous emulsion of polyorganosiloxane. Finally, 725 g of ion-exchanged water and 2.3 g of potassium persulfate are dissolved in the aqueous emulsion of polyorganosiloxane obtained above, transferred to a flask, and heated to 70 ° C. while flowing nitrogen into the flask. 224.9 g (1.61 mol) of trifluoroacetate were slowly added dropwise. After completion of the dropwise addition, the mixture was aged for 3 hours to obtain an aqueous emulsion of the graft copolymer.

Production Example 8 97.7 g of octamethylcyclotetrasiloxane (0.
33 mol) and 1.8 g of hexamethyldisiloxane (1
1.1 mmol), 3.2 g (13.8 mmol) of γ-methacryloxypropylmethyldimethoxysilane, and 2.8 g of dodecylbenzenesulfonic acid in ion-exchanged water 234.
g, and an aqueous emulsion of polyorganosiloxane was obtained in the same manner as in Production Example 1. Then, the aqueous emulsion of polyorganosiloxane obtained above, 2.5 g of potassium persulfate, 967.5 g of ion-exchanged water, 50.0 g (0.50 mol) of methyl methacrylate and 4-
Using 25.0 g (0.20 mol) of fluorostyrene,
An aqueous emulsion of the graft copolymer was obtained in the same manner as in Production Example 1.

Production Example 9 The aqueous emulsion of the polyorganosiloxane obtained in Production Example 4 was charged into a flask, and 1.6 g of potassium persulfate, 735 g of ion-exchanged water, and 25.0 g of 4-fluorostyrene were prepared.
(0.2 mol), acrylonitrile 25.0 g (0.4
7 mol) to obtain an aqueous emulsion of a graft copolymer in the same manner as in Production Example 1.

Production Example 10 An aqueous emulsion of the polyorganosiloxane obtained in Production Example 5 was charged into a flask, and a solution prepared by dissolving 1.5 g of potassium persulfate in 483 g of ion-exchanged water was added thereto. The mixture was heated to 70 ° C., and 100 g (0.59 mol) of trifluoroethyl methacrylate was slowly added dropwise. After completion of the dropwise addition, the mixture was aged for 3 hours to obtain an aqueous emulsion of the graft copolymer.

Production Example 11 Linear polydimethylsiloxane (average molecular weight: 1000)
0) 15 g, sodium dodecylbenzenesulfonate 2
g was dissolved in 88 g of ion-exchanged water and emulsified with a homogenizer to obtain an aqueous emulsion.

Production Example 12 100 g of methacrylate-modified polydimethylsiloxane (average molecular weight: 5,000) at one end was dissolved in 500 g of xylene, charged into a flask together with 0.2 g of azobisisobutylnitrile, and heated to 70 ° C. After the atmosphere in the flask was replaced with nitrogen, 100 g of methyl methacrylate was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was aged at 80 ° C. for 4 hours. After completion of aging, the mixture was gradually cooled, reprecipitated with excess methanol, and filtered. 100 g of the solid obtained by drying the filtered solid was added to 850 g of ion-exchanged water in which 50 g of sodium dodecylsulfonate was dissolved, and the mixture was emulsified with a homogenizer to obtain an aqueous emulsion.

[0038]

[Table 1]

Test Category 2 Examples 1 to 10 and Comparative Examples 1 to 3 Polyethylene terephthalate having an intrinsic viscosity of 0.62 measured in orthochlorophenol at 25 ° C. and containing no inorganic filler was used as an extruder. And extruded from a die, applying a static electricity on a drum cooled to 40 ° C. to form an extruded film having a thickness of 152 μ,
Subsequently, on a metal roll heated to 93 ° C. in the longitudinal direction.
The film was stretched 6 times to obtain a uniaxially stretched film. Next, at a position immediately before the uniaxially stretched film reached the tenter, the aqueous emulsion produced in Test Section 1 was uniformly applied to one surface of the uniaxially stretched film 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} 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 guided into a tenter, stretched 3.5 times in the transverse direction at 101 ° C., and further heat-set at 225 ° C. for 6.3 seconds to obtain a biaxially stretched film (one side). The total time for which the applied film was heated was 11 seconds). The biaxially stretched film could be wound up at 9.8 kg tension without wrinkling. The biaxially stretched film was micro-slit to 1/2 inch width to produce 52 tapes of 500 mg winding. During this time, the micro-slit formation could be performed without any problem. Table 2 summarizes the applicability of the aqueous emulsion produced in Test Category 1, the appearance of the biaxially stretched film, the contact angle of water droplets, the coefficient of friction, and the releasability. These were 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. evaluated. ；: No plaque is observed at all △: Slight mottling is observed ×: Marked mottling is observed

Film appearance: 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 the unprocessed film ；: one part has poor transparency, ×: the entire surface is opaque

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

Coefficient of friction: 23 ° C. × 6 for biaxially stretched film
The humidity was adjusted in an atmosphere of 5% RH, and under the same conditions, the coefficient of friction (μd) of the matte surface against the stainless steel plate was measured using a friction coefficient measuring device (TR type manufactured by Toyo Seiki Co., Ltd., load 200 g, speed 300 mm
/ Min).

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

[0045]

[Table 2]

[0046]

As is apparent from the above description, the present invention described above can be applied to a polyethylene terephthalate film or a polyethylene terephthalate sheet without special equipment, economically, without toxicity, and with high smoothness. There is an effect that surface characteristics such as water repellency, water repellency, oil repellency, releasability, and stain resistance can be imparted.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-131537 (JP, A) JP-A-3-99827 (JP, A) JP-A-2-269133 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08J ^7/ 04-7/06 B32B 27/00-27/42

Claims (4)

(57) [Claims] 1. A polyethylene terephthalate film comprising an aqueous emulsion of a graft copolymer represented by the following formula 1, wherein the average particle diameter of the graft copolymer particles is 0.01 to 0.5 μm: Or po
A polyethylene terephthalate film or a poly ( ethylene terephthalate) film coated on a polyethylene terephthalate sheet
A method for treating a tylene terephthalate sheet. (Equation 1) Wherein R ^{1 to} R ³ each have a carbon atom directly bonded to a silicon atom, and are the same or different, unsubstituted or substituted,
Hydrocarbon groups having no radical polymerizability. A: having a carbon atom directly bonded to a silicon atom, and B
A divalent organic group linked to B: Vinyl monomer block or vinyl polymer block. T ¹ , T ² : a silyl terminal group represented by the following formula 2 or 3. (Equation 2) (Equation 3) (R ⁴ ~R ^8: same .Y as for ^{R 1 ~R 3: A-B} , H or OH.) A: 50 to 4000 integer. b: Integer satisfying 1 ≦ b ≦ a / 20. The siloxane unit formed by a and the siloxane unit formed by b are bonded in a block or random manner. ] 2. Graft polymerization or grafting of a vinyl monomer in which B of the formula 1 contains 90% by weight or more of one or more selected from aromatic vinyl monomers, alkyl (meth) acrylates and acrylonitrile. 2. The polyether according to claim 1, which is a vinyl polymer block obtained by copolymerization.
Tylene terephthalate film or polyethylene tereph
How to process tarate sheets. 3. A method according to claim 1, wherein B of the formula (1) is obtained by grafting 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. 2. The polypolymer according to claim 1, which is a vinyl polymer block obtained by polymerization or graft copolymerization.
Polyethylene terephthalate film or polyethylene
Processing method of phthalate sheet. 4. A vinyl monomer having a fluorine substituent in which B in the formula 1 is an aromatic vinyl monomer, a vinyl carboxylate, and an alkyl (meth) each having a fluorine substituent.
2% by weight of one or more selected from acrylates
The polyethylene terephthalate film according to claim 3, which is a vinyl polymer block obtained by graft polymerization or graft copolymerization of a vinyl monomer containing the above.
A method for treating a polyethylene terephthalate sheet.