JP3040805B2 - Thermoplastic resin film with improved lubrication and anti-blocking properties - Google Patents

Description

The present invention relates to a thermoplastic resin film having improved lubricity and anti-blocking property. Films made from resin compositions containing various thermoplastic resins as the main components, such as polyolefin, polyester, polyvinyl chloride, polyamide, and polystyrene, are used for packaging materials, photographs, magnetic recording media, capacitors, etc. Are widely used as industrial base films, but in recent years, with the diversification of these base films and the advancement of their functions, demands for improving the surface properties of the base films have been increasing. For example, in the field of magnetic recording media in which a base film formed from a resin composition containing a linear aromatic polyester as a main component is used, the recording density, capacity, and reliability have been increasing with the increase in recording density. In addition, there is a strong demand for providing the base film with better lubricity as the base film becomes thinner. Also, in the field of packaging materials in which a base film formed from a resin composition containing polyolefin as a main component is used, kneading is performed to impart antistatic properties, printability, anti-fog properties, and the like to the base film. The surfactant or hydrophilic polymer compound to be incorporated or applied promotes the blocking property between the film surfaces, and therefore, there is a strong demand for imparting an anti-blocking property to the base film.

The present invention relates to a new thermoplastic resin film that meets the above-mentioned requirements by containing specific spherical composite fine particles.

<Prior art and its problems> Conventionally, as means for imparting lubricity or anti-blocking property to a thermoplastic resin film, 1) a catalyst used in the synthesis of a polymer which is a main component of the thermoplastic resin film, etc. 2) means for adding inert particles such as calcium carbonate and clay (JP-A-52-3645, JP-B-59-8216), 3) silica, titania, organic poly Means for adding spherical fine particles such as siloxane (JP-A-59-171623, JP-A-62-172031,
JP-A-62-207356 and JP-A-63-178144) have been proposed.

However, the conventional means of 1) has a problem that it is difficult to control the deposited fine particles because the shapes, sizes, amounts, etc. thereof are not uniform. In the conventional method 2), it is difficult to completely inactivate the surface of the particles, and therefore, there is a problem that a part of the particles react with the polymer to cause coloring. As a result of generating coarse particles between each other, clogging of the filter in the film forming process, tearing of the film, fish eyes and the like are likely to occur,
Further, there is a problem that when a formed base film is used as a magnetic tape, dropout or the like is apt to occur.
The conventional means of 3) has a problem that spherical fine particles are likely to aggregate to form coarse particles. Therefore, in actual addition, it is necessary to disintegrate the aggregated spherical fine particles. Since many spherical fine particles are broken by mechanical external force at the time of crushing, there is a problem that as a result, many irregular shaped particles are added.

After all, any conventional means does not adversely affect the intrinsic properties of the thermoplastic resin film, which is the base film, and has good lubricity and anti-blocking properties as recently required for thermoplastic resin films. Cannot be given.

<Problems to be Solved by the Invention, Means for Solving the Problems> The present invention is to solve the above-mentioned conventional problems and to provide a new thermoplastic resin film which meets the above-mentioned requirements.

Thus, the present inventors have conducted intensive studies in view of the above, and as a result, have obtained a specific spherical composite fine particle formed from a copolymer in which a specific polysiloxane block and a specific vinyl polymer block are mutually cross-linked. A thermoplastic resin film containing a predetermined amount was found to be properly suitable,
The present invention has been completed.

That is, the present invention, the following spherical composite fine particles 0.005 ~
The present invention relates to a thermoplastic resin film having improved lubricity and anti-blocking property, characterized by comprising 5% by weight.

Spherical composite fine particles: spherical particles formed from a copolymer in which a polysiloxane block of the following (I) and a vinyl polymer block of the following (II) are cross-linked to each other using R ³ in the polysiloxane block as a linking hand. Composite fine particles,
And the polysiloxane block / the vinyl polymer block is 97/3 to 20/80 (weight ratio), and the average particle size is 0.05 to 5
μm, spherical composite fine particles having a standard deviation of particle size distribution of 1.0 to 2.5, and a ratio of major axis to minor axis of 1.0 to 1.2.

(I): 99.9 to 0 mol% of one or more structural units represented by the general formula [R ¹ _a SiO _{(4-a) / 2} ] and the general formula [R ² _m R ³ _n SiO _{(4) -Mn) / 2} ] is a polysiloxane block composed of 0.1 to 100 mol% of structural units represented by the formula (1) and wherein a is 1 or less and / or m + n is 1. A polysiloxane block containing 15 mol% or more of structural units in total.

[However, a is an integer of 0 to 3. m is an integer of 0 to 2, n is 1
An integer satisfying 1 ≦ m + n ≦ 3.
R ¹ and R ² are the same or different unsubstituted or substituted non-radical polymerizable hydrocarbon groups having a carbon atom directly bonded to a silicon atom. R ³ is a group represented by AB. A is an alkylene group having 2 or 3 carbon atoms directly bonded to a silicon atom.
B is a direct bond or One or more selected from (b is an integer of 0 to 3). ｝. (II): a vinyl polymer block obtained by polymerizing one or more kinds of radically polymerizable vinyl monomers containing an ethylenically unsaturated group.

The thermoplastic resin film of the present invention is a film formed from a resin composition containing a thermoplastic resin as a main component.
Specifically, a linear aromatic polyester film, a polyamide film, a polyolefin film obtained from a homopolymer of ethylene or propylene or a copolymer based on them, a polystyrene film obtained from a homopolymer of styrene or a copolymer based on the same And a polyvinyl chloride film obtained from a homopolymer of vinyl chloride or a copolymer mainly composed of the same. Among them, linear aromatic polyester films, polyamide films, and polyolefin films are useful for the purpose.

The linear aromatic polyester film may be any film as long as it can be obtained from a polyester that can be molded as a film.Specific examples of such polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene-p-oxybenzoate, In addition to homopolyesters such as poly-1,4-cyclohexylene dimethylene terephthalate and polyethylene 2,6-naphthalenedicarboxylate, there are copolymerized polyesters. And the copolymerization component at the time of synthesizing such a copolymerized polyester, diol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, adipic acid, sebacic acid, phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, There are dicarboxylic acid components such as 5-sodium sulfoisophthalic acid, and polyfunctional carboxylic acid components such as trimellitic acid and pyromellitic acid. The polyamide film may be any polyamide as long as it can be obtained from a polyamide that can be molded as a film, and such polyamide is 6-nylon or a main component thereof. The density and molecular three-dimensional structure of the polyolefin film are not particularly limited, and any film obtained from a polyolefin that can be formed into a film may be used.

In the spherical composite fine particles used in the present invention, the average particle diameter is arbitrarily selected from 50 particles from electron micrographs,
Calculated by measuring the major axis (longest diameter passing through the center of the particle = D _L ) and minor axis (shortest diameter passing through the center of the particle = D _S ) / 2 for each of the selected individual particles (D _L + D _s ) / 2 And the ratio between the major axis and the minor axis is the average value of D _L / D _s calculated in the same manner. The standard deviation value of the particle size distribution is a value obtained by particle size distribution measurement using an ultracentrifugal sedimentation system. The spherical composite fine particles have an average particle size of 0.05 to 5 μm, a standard deviation of the particle size distribution is in a range of 1.0 to 2.5, and a ratio of a major axis to a minor axis is in a range of 1.0 to 1.2, The ratio between the major axis and minor axis is
Although it is spherical because it is in the range of 1.0 to 1.2, among these, the average particle size is suitably 0.1 to 3 μm, and the standard deviation of the particle size distribution is in the range of 1.0 to 2.0, Further, those having a ratio of the major axis to the minor axis in the range of 1.0 to 1.1 are preferable.

The polysiloxane block, which is a block of the copolymer forming the spherical composite fine particles used in the present invention, is one or two structural units represented by any one of the above two general formulas (I).
A polysiloxane block comprising at least one species, and wherein a in the general formula is 1 or less and / or m +
n is a polysiloxane block containing at least 15 mol% of the constituent units of 1 in total. Specifically, [SiO ₂ ], [R ^{1
_{SiO 3/2], [R 1 2}} SiO] or [R ¹ ₃ 1 types of structural units represented by SiO _1/2] or more is 99.9 to 0 mol%, and [R ³
SiO _3/2 ], [R ³ ₂ SiO], [R ² R ³ SiO], [R ³ ₃ SiO _1/2 ],
^{_{[R 2 R 3 2 SiO 1/2}} ] or ^{_{[R 2 2 R 3 SiO 1/2}} ] in one or more of the structural units represented 0.1 to 100 mol%, preferably 0.
A polysiloxane block composed of 1 to 60 mol%, and a is 1 or less, ie, one or two of the structural units represented by [SiO ₂ ] or [R ¹ SiO _3/2 ], and / or Alternatively, it is a polysiloxane block containing a total of 15 mol% or more, preferably 20 mol% or more of structural units represented by [R ³ SiO _3/2 ] in which m + n is 1. If the sum of the constituent units having a of 1 or less and / or the constituent units having m + n of 1 is less than 15 mol%, spherical composite fine particles having the above-described characteristics relating to the particle diameter cannot be obtained.

In the structural unit of the polysiloxane block as described above, R ¹ and R ^{2 each} have a carbon atom directly bonded to a silicon atom, and are the same or different unsubstituted or substituted hydrocarbon groups at the same time. It is a hydrocarbon group having no radical polymerizability.

Examples of R ¹ and R ² in the case of an unsubstituted hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an aralkyl group and the like, and among them, a methyl group, an ethyl group, and a butyl group An alkyl group having 1 to 4 carbon atoms or a phenyl group is advantageously selected. Further, when R ¹ and R ² are a substituted hydrocarbon group, examples of the substituent include a substituted hydrocarbon group having a halogen, an epoxy group, a cyano group, a ureido group, etc., and among them, γ-glycidoxy is preferred. Propyl, 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 structural unit of the polysiloxane block as described above, R ³ is an alkylene group having 2 or 3 carbon atoms directly bonded to a silicon atom, or an organic group having the alkylene group. R ³ is derived from an ethylenically unsaturated group or a mercapto group, for example, a vinyl group, an allyl group, an acryloxypropyl group, a methacryloxypropyl group or a mercaptopropyl group, and a polysiloxane block and a vinyl polymer block. It is important as a connecting hand that crosses each other.

The vinyl polymer block which is another block of the copolymer forming the spherical composite fine particles used in the present invention is the above-mentioned (I)
As I), it is a vinyl polymer block obtained by polymerizing one or more vinyl monomers having a radical polymerizable ethylenically unsaturated group.

Examples of the vinyl polymer block as described above include polystyrene, an aromatic vinyl polymer block such as poly α-methylstyrene, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyvinyl acetate, vinyl polypropionate, and polyacrylonitrile. Such as aliphatic vinyl polymer blocks, styrene / α-methylstyrene copolymer, styrene / acrylonitrile copolymer, styrene / methyl methacrylate copolymer, and styrene / divinylbenzene copolymer And a crosslinked vinyl copolymer block such as methyl methacrylate / trimethylolpropane trimethacrylate copolymer. Among them, an aromatic vinyl polymer block obtained by polymerizing styrene, α-methylstyrene, etc. Aliphatic vinyl polymer block obtained by polymerizing an alkyl ester of acrylic acid or acrylic acid are advantageously selected.

As the vinyl polymer block in the present invention, in addition to the vinyl polymer block obtained by polymerizing the water-insoluble vinyl monomer as exemplified above, a water-insoluble vinyl monomer and a water-soluble vinyl monomer And vinyl copolymer blocks such as styrene / sodium styrene sulfonate copolymer, methyl methacrylate / acrylic acid copolymer, methyl methacrylate / polyethylene glycol methacrylate copolymer, and water-soluble vinyl monomer. Contains vinyl polymer blocks such as polyacrylamide, polyacrylic acid and sodium polystyrenesulfonate obtained by polymerizing the monomer, and also contains reactive organic groups such as epoxy group, amino group, carboxyl group and hydroxyl group. Methyl methacrylate / glycidyl methacrylate copolymer, styrene On / maleic anhydride copolymer, vinyl polymer block such as methyl methacrylate / 2-hydroxyethyl methacrylate copolymer.

The spherical composite fine particles used in the present invention are obtained from a copolymer in which the polysiloxane block (I) and the vinyl polymer block (II) are cross-linked to each other by using R ³ in the polysiloxane block as a link. The polysiloxane block / the vinyl polymer block has a weight ratio of 97/3 to 20/80. If the ratio of the polysiloxane block is higher than this range, the resulting spherical composite fine particles are liable to be broken by mechanical impact, and the dispersibility in the polymer material is deteriorated. Conversely, if the ratio of the vinyl polymer block is higher than this range, the low energy characteristics of the resulting spherical composite fine particles due to the polysiloxane will be reduced.

Next, a method for producing the spherical composite fine particles used in the present invention will be described. Spherical composite fine particles used in the present invention,
It can be roughly classified into four types of methods.

The first method (hereinafter, referred to as Method A) is a method in which a silanol group-forming silicon compound of the following (III) and a vinyl monomer of the following (IV) are converted into a silanol group-forming silicon compound of the following (III):
The vinyl monomer of (IV) is used in a ratio of 99/1 to 22/78 (weight ratio), and is first used in an aqueous medium in which both coexist (III)
Condensation polymerization while hydrolyzing the silanol group-forming silicon compound of formula (IV) to form polysiloxane spherical fine particles containing a vinyl monomer of (IV), and then radical polymerization in an aqueous medium in which the spherical fine particles are dispersed. This is a method of grafting while polymerizing the vinyl monomer (IV) in the presence of a catalyst.

(III): one or more of the silanol group-forming silicon compounds represented by the general formula (V) or (VI) is 99.0-0
Mol% and at least one silanol group-forming silicon compound represented by the general formula (VII) or (VIII) is 0.1% or less.
A silanol group-forming silicon compound having a total content of 15 mol% or more, wherein the silanol group-forming silicon compound has a p of 1 or less and / or a silanol group-forming silicon compound having an r + s of 1 R ⁴ _p -SiX _(4-p) General formula (VI); General formula (VII); R ⁷ _r R ⁸ _s SiX _(4-rs) General formula _(VIII) ; [However, p is an integer of 0-3. r is an integer of 0 to 2, s is 1
An integer satisfying 1 ≦ r + s ≦ 3;
q and t are integers from 3 to 20. R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different unsubstituted or substituted non-radical polymerizable hydrocarbon groups having a carbon atom directly bonded to a silicon atom. R ⁸ and R ⁹ are --CH
= CH _2, Or two or more selected from (y is an integer of 2 or 3, z is an integer of 0 to 3). R ¹⁰ is the same hydrocarbon group as R ⁴ , R ⁵ , R ⁶ and R ⁷ or the same organic group as R ⁸ and R ⁹ . X has 1 to 1 carbon atoms
An alkoxy group having 4 alkoxy groups, an alkoxyethoxy group having an alkoxy group having 1 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an N, N-dialkylamino group having an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and a halogen atom Atom or hydrogen atom. (IV): One or more vinyl monomers containing a radically polymerizable ethylenically unsaturated group.

In the second method (hereinafter referred to as Method B), the silanol group-forming silicon compound of (III) and the vinyl monomer of (IV) are combined with the silanol group-forming silicon compound of (III) /
The vinyl monomer of (IV) is used in a ratio of 99/1 to 22/78 (weight ratio), and is subjected to condensation polymerization while hydrolyzing the silanol group-forming silicon compound of (III) in an aqueous medium. This is a method in which spherical fine particles of polysiloxane are generated, and then a vinyl monomer (IV) is added to an aqueous medium in which the spherical fine particles are dispersed, and grafting is performed while polymerizing in the presence of a radical polymerization catalyst.

The third method (hereinafter referred to as method C) is represented by the above general formula (V), (VI), (VII) or (VIII) which forms the silanol group-forming silicon compound of the above (III). Silanol group-forming silicon compound and (IV)
The vinyl monomer of (III) is used in a ratio of the silanol group-forming silicon compound of (III) / the vinyl monomer of (IV) of 99/1 to 22/78 (weight ratio). (V)
Alternatively, the silanol group-forming silicon compound represented by (VI) is hydrolyzed and polycondensed by hydrolysis to form primary spherical fine particles of polysiloxane, and then into a water-based medium in which the primary spherical fine particles are dispersed, represented by the general formula (VII): In the other method, after adding a silanol group-forming silicon compound represented by (VIII) and reacting to generate spherical fine particles, the vinyl monomer of (IV) is further added to an aqueous medium in which the spherical fine particles are dispersed. And grafting while polymerizing in the presence of a radical polymerization catalyst.

The fourth method (hereinafter referred to as method D) is represented by the above general formula (V), (VI), (VII) or (VIII), which forms the silanol group-forming silicon compound of the above (III). Silanol group-forming silicon compound and (IV)
The vinyl monomer of (III) is used in a ratio of the silanol group-forming silicon compound of (III) / the vinyl monomer of (IV) of 99/1 to 22/78 (weight ratio). (V)
Alternatively, the silanol group-forming silicon compound represented by (VI) is hydrolyzed and polycondensed by hydrolysis to form primary spherical fine particles of polysiloxane, and then into a water-based medium in which the primary spherical fine particles are dispersed, represented by the general formula (VII): Or adding the silanol group-forming silicon compound represented by (VIII) and the vinyl monomer of (IV) to react with the silanol group-forming silicon compound represented by the general formula (VII) or (VIII) and (IV) Is a method in which a vinyl monomer is grafted while being polymerized in the presence of a radical polymerization catalyst.

According to the method for producing the spherical composite fine particles used in the present invention, the following two reactions can partially proceed at the same time depending on the method, but the reaction for producing a polysiloxane and the reaction for producing a vinyl polymer are largely different. Separated.

In the reaction for producing the polysiloxane, the above-mentioned silanol group-forming silicon compound as the raw material for the polysiloxane is added to the aqueous system in the presence or absence of the vinyl monomer as the raw material for the vinyl polymer. Polycondensates while hydrolyzing in the medium. The catalyst used for condensation polymerization while hydrolyzing the silanol group-forming silicon compound may be a conventionally known catalyst.

The reaction of polycondensation while hydrolyzing is carried out by charging a silanol group-forming silicon compound and, depending on the production method, a vinyl monomer into an aqueous medium in which a catalyst is dissolved, followed by stirring. The temperature and time for polycondensation while hydrolyzing,
Depending on the type and concentration of the raw materials, the type of solvent, the type and concentration of the catalyst, etc., the temperature is usually 0 to 90 ° C, preferably 0 to 60 ° C.
° C, and times are usually in the range of 30 minutes to 24 hours. Thus, polysiloxane is formed, and spherical fine particles of the polysiloxane are obtained.

In the reaction for forming a vinyl polymer, grafting is performed while polymerizing a vinyl monomer in an aqueous medium in which spherical fine particles of polysiloxane are dispersed in the presence of a radical polymerization catalyst. Various methods are possible for the transition from the reaction for producing the polysiloxane to the reaction for producing the vinyl polymer. For example, if the catalyst used in the reaction for producing the polysiloxane has no problem in the reaction for producing the vinyl polymer, it can be transferred as it is, and if there is a problem, the catalyst is removed or inactivated. Migrate from The aqueous medium in the reaction for producing the vinyl polymer is the same as the aqueous medium in the reaction for producing the polysiloxane, but here, it is preferable to use a solvent of water alone. A conventionally known radical polymerization catalyst may be used for grafting while polymerizing a vinyl monomer.

The reaction of grafting while polymerizing the vinyl monomer is performed by stirring an aqueous medium in which the vinyl monomer and polysiloxane spherical fine particles are dispersed in an inert gas atmosphere in the presence of a radical polymerization catalyst. Do. The temperature at this time varies depending on various conditions as in the case of the reaction for producing the polysiloxane, but is usually in the range of room temperature to the boiling point of the vinyl monomer, preferably 50 to 80 ° C. Thus, a desired spherical composite fine particle formed from a copolymer in which a polysiloxane block and a vinyl polymer block are cross-linked to each other by forming a vinyl polymer, that is, grafting while polymerizing a vinyl monomer. Get.

The average particle diameter of the resulting spherical composite fine particles, the standard deviation value of the particle diameter distribution and the ratio of the major axis to the minor axis are determined by the type and concentration of the raw materials used, the type of solvent, the type and concentration of the catalyst, and further the reaction temperature and reaction. It depends on time and the like, and can be adjusted by appropriately selecting these conditions. It can also be adjusted by crushing, dispersing, and classifying the obtained spherical composite fine particles by a dry or wet method.

The thermoplastic resin film of the present invention contains the above-mentioned spherical composite fine particles in an amount of 0.005 to 5% by weight. When the characteristic value related to the particle diameter of the spherical composite fine particles deviates from the above-described range, or when the content of the spherical composite fine particles deviates from the above range, the desired effect of improving the slipperiness and the anti-blocking property is not obtained or is obtained. The use of the thermoplastic resin film itself or the thermoplastic resin film for various uses has an adverse effect. For example, when a thermoplastic resin film having the above-mentioned characteristic values or contents deviating from a predetermined range is used in the field of a magnetic recording medium, it affects the thickness of a magnetic layer applied to the thermoplastic resin film and affects the thickness. It degrades the electrical properties. In this sense, regarding the characteristic value related to the particle size of the spherical composite fine particles,
Average particle size is 0.1 ~ 3μm, standard deviation of particle size distribution is 1.0 ~
2.0, the ratio of the major axis to the minor axis is preferably 1.0 to 1.1, and the content of the spherical composite fine particles is 0.05 to
It is preferably 3% by weight, more preferably 0.1 to 1% by weight.

In order to make the thermoplastic resin film contain the spherical composite fine particles, the polymer before film formation, which is the main component of the thermoplastic resin film, contains the spherical composite fine particles. The means for containing is not particularly limited. The spherical composite fine particles may be mixed and dispersed so as to have a predetermined concentration in the polymer in the molten state, or the spherical composite fine particles may be added and kneaded so as to have a concentration higher than the predetermined concentration in the polymer in the molten state. The polymer may be diluted during film formation, or may be added and dispersed in a polymer having a low melt viscosity at the stage of low melt viscosity, followed by polymerization. In the case of producing a linear aromatic polyester film or a polyamide film, it is effective to add and disperse spherical composite fine particles during the polymerization of those polymers, especially when producing a linear aromatic polyester film. It is preferable to disperse the spherical composite fine particles in advance in an alkylene glycol such as ethylene glycol or 1,4-butanediol, and then to add and disperse them in a polymer polymerization system. More preferably, the secondary aggregated particles are crushed in alkylene glycol to form primary particles and then added to the polymer polymerization system.

The thermoplastic resin film of the present invention contains a predetermined amount of specific spherical composite fine particles, but other additives such as an ultraviolet absorber, an antioxidant, and an antistatic agent as long as the effects of the present invention are not impaired. Can also be contained.

The thermoplastic resin film of the present invention is produced from a resin composition containing a thermoplastic resin containing specific spherical composite fine particles as a main component, by a conventional method such as an inflation method, a casting method, a uniaxial stretching method, and a biaxial stretching method. You. The thermoplastic resin film may be laminated with another film, or may be coated with a coating agent, or may be subjected to a high degree of physical, chemical and / or electrical treatment, depending on various uses. It is used specifically.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to the examples.

<Examples and the like> Test Category 1 (Production of spherical composite fine particles) Fine particles 1 which are spherical composite fine particles used in the present invention are described below.
And the contents and results thereof are shown in Table 1 together with the fine particles 2 to 8 produced in the same manner.

The contents and results in Table 1 were measured by the following methods.

1) Average particle diameter and ratio of major axis to minor axis The spherical composite fine particles and the like obtained in each example were photographed with a scanning electron microscope (SEM). The shortest diameter passing through the center of the photographing image arbitrarily selected 50 particles from the (longest diameter = D _L passing through the center of the particle) Selection was longer diameter of the individual particles and the minor axis (particles = D _S ) was measured and calculated (D _L
The average value of + D _S ) / 2 was defined as the average particle size, and the average value of D _L / D _S was defined as the ratio of the major axis to the minor axis.

2) Standard deviation value of particle size distribution The spherical composite fine particles and the like obtained in each example are ultrasonically dispersed in water containing 1% by weight of a 10 mol adduct of nonylphenol ethylene oxide, and an ultracentrifugal automatic dispersion is performed using the dispersion. The average particle size and the particle size distribution were measured with a particle size distribution measuring device (CAPA-700 manufactured by Dig Seisakusho Co., Ltd.). The value obtained by dividing the sum of the standard deviation of the particle size distribution and the average particle size by the average particle size was defined as the standard deviation value of the particle size distribution.

3) Polysiloxane content (% by weight) After the spherical composite fine particles obtained in each example were heated and dried in a nitric acid / perchloric acid (5/2) mixture to decompose organic substances,
Molybten blue method (colorimetric method; Anal. Chem., 19, 873, 194)
Seeking SiO ₂ content of 7 years) was a value calculated from its SiO2 content and the charged composition ratios of silicon compound and a polysiloxane content.

・ Production of fine particles 1 In a flask, 658 ml of water and 8.3 g of 28% aqueous ammonia were charged, and at room temperature, 6 g (0.029 mol) of ethyl orthosilicate and octamethylcyclotetraethyl were slowly stirred while keeping the contents in a two-layer state. 23 g (0.078 mol) of siloxane,
A mixture of 69 g (0.51 mol) of trimethoxymethylsilane, 2 g (0.0081 mol) of γ-methacryloxypropyltrimethoxysilane and 10 g (0.096 mol) of styrene was added dropwise over 1 hour, and hydrolyzed at the solution interface in a two-layer state. Polycondensation occurred during the polymerization. As the reaction proceeded, the product gradually settled to the lower layer, and the lower layer became cloudy, but after about 2 hours, the two-layer state disappeared and became a homogeneous system. Subsequently, the mixture was stirred at room temperature for 2 hours, further at 60 ° C. for 3 hours, cooled to room temperature, and the generated white fine particles were separated by filtration. Next, the white fine particles were charged into another flask together with 965 g of ion-exchanged water, dispersed in a homomixer, and then heated to 70 ° C. under a nitrogen stream,
50 g of a 3% aqueous potassium persulfate solution was added dropwise over 1 hour. After aging at 70 ° C. for 3 hours to carry out radical polymerization, the content was cooled to room temperature, and white composite fine particles were separated by filtration. Then, the white composite fine particles are washed and dried,
60.2 g of spherical composite fine particles were obtained.

The resulting spherical composite fine particles have an average particle size of 1.0 μm, a ratio of the major axis to the minor axis of 1.04, and the standard deviation of the particle size distribution is 1.49,
The polysiloxane content was 86.8% by weight.

Hereinafter, fine particles 2 to 13 were produced by the above-described A to D methods. Table 1 shows these contents, including the case of fine particles 1,
The results are shown in Table 2.

Test Category 2 (Production of Dispersion) Dispersions 1 to 11 of the spherical composite fine particles used in the present invention are described below.
And methods for producing dispersions A to D for comparison, and their contents and results are summarized in Table 3.

The results in Table 3 were evaluated by the following methods.

1) Shape Retention For each of the obtained dispersions, 50 fine particles were arbitrarily selected from the image taken by the electron microscope described above, and the presence or absence of breakage of each selected fine particle was observed. Was evaluated.

◎: 1 or less broken particles observed ○: 2 to 6 broken particles observed △: 7 to 24 broken particles observed ×: 25 or more broken particles observed 2) Aggregated particles The presence or absence of each obtained dispersion was observed with an optical microscope of 1000 times, and
The degree of aggregation of the fine particles present in the range of × 20 μm was evaluated according to the following criteria.

○: Aggregated particles are less than 1% of all particles △: Aggregated particles are 1% or more and less than 10% of all particles ×: Aggregated particles are 10% or more of all particles 3) Dispersion stability Each obtained dispersion is conical. Put in a glass container, leave it tightly closed at room temperature, observe the separation state of fine particles daily,
Evaluation was made according to the following criteria.

◎: No separation of fine particles was observed even after one month ○: Separation of fine particles was observed from 7 days to January △: Separation of fine particles was observed from 2 days to 6 days ×: Separation of fine particles was 1 The process was carried out after 1 day. Preparation of Dispersions 1 to 11 and A to D 40 g of the fine particles shown in Table 3 and ethylene glycol in such an amount that the fine particles had a predetermined concentration were weighed and predispersed with a homomixer. Batch type sand grinder using glass beads of 0.60-0.85mmφ (manufactured by Igarashi Kikai Co., Ltd.
Disperse 1 to 13 by treating with a vessel capacity of 400 cc) for 5 hours.
And AD.

Test Category 3 Examples and comparative examples of the present invention are given below, and their contents and results are summarized in Tables 4 and 5.

The results in Tables 4 and 5 were evaluated by the following methods.

1) Presence or Absence of Agglomerated Particles Each of the produced films was photographed by an electron microscope as described above, and the image was observed in a range of 70 × 50 μm and evaluated according to the following criteria.

○: no aggregated particles existed △: aggregated particles existed slightly ×: aggregated particles existed in 10% or more of all particles 2) Presence / absence of voids Observation of the image of 1) above shows voids around fine particles Was determined.

3) Slippery A 13 mm wide tape-shaped sample was prepared from each of the produced films, and this sample was brought into contact with a stainless steel rod fixing pin (7 mmφ) with an incoming load of 30 g, and was reciprocated 30 times at 2.5 m / min. Was. The coefficient of friction after 30 reciprocations was measured using a friction coefficient measuring device (TR type manufactured by Toyo Seiki Co., Ltd., load 200 g, speed 300 mm / min), and the surface condition of the sample after 30 reciprocations was visually observed. It was observed and evaluated as an index of wear resistance according to the following criteria.

Evaluation criteria for abrasion resistance ◎: No change such as whitening or scratches is observed ○: Slight whitening or scratches are observed △: Clear whitening or scratches are seen ×: Remarkable whitening or scratches are found ・ Examples 1 to 5 and Comparative Examples 1 to 4 Using 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol and 0.035 parts by weight of manganese acetate tetrahydrate, the temperature was raised to 230 ° C. according to a conventional method to carry out a transesterification reaction. . Next, after adding 0.03 parts by weight of trimethyl phosphate, the dispersions shown in Table 3 were added so that the content of the spherical composite fine particles and the like became a predetermined amount with respect to the polymer, followed by stirring. After 0.03 parts by weight of antimony trioxide was added, the temperature was raised, and a polycondensation reaction was performed under a high temperature and a high vacuum according to a conventional method to obtain polyethylene terephthalate having an intrinsic viscosity of 0.61 dl / g. The polyethylene terephthalate obtained here was dried at 180 ° C., formed into a sheet with an extruder set at 290 ° C., and then 3.5 parts in the vertical direction at 90 ° C. and in the horizontal direction.
The film was stretched 4.0 times and heat-set at 210 ° C. to produce a film having a thickness of 15 μm.

Test Category 3 (Example of use of spherical composite fine particles) Examples 6 to 8 and Comparative Examples 5 to 6 200 parts by weight of ε-caprolactam, 6 parts by weight of water, and 0.0 part of acetic acid
29 parts by weight and the amount of the fine particles shown in Table 5 in which the content becomes a predetermined amount with respect to the polymer were charged into a polymerization vessel, sealed after being replaced with nitrogen gas, and kept at 260 ° C. When the internal pressure reaches 3.5 kg / cm ² , a part of the water in the can is removed and the internal pressure is reduced to 3.5 k
The reaction was performed for 3 hours while maintaining the g / cm ² . Then
The pressure was gradually released over 1 hour to normal pressure, and the polymerization was further advanced in a nitrogen gas stream for 3 hours to obtain a polyamide. The relative viscosity of the polyamide obtained here was 2.60.

The above polyamide was extracted from a T-die at 250 ° C. with an extruder having a diameter of 30 mm, and was solidified by cooling at 110 ° C. with a casting roll to produce a film having a thickness of 40 μm.

Examples 9 to 11 Three types of fine particles 2, 4 or 8, polyethylene resin (Yukaron LF-540B, manufactured by Mitsubishi Yuka Co., Ltd.) and antistatic agent (glycerin monostearate / N, N-bishydroxyethyllaurylamine (Mixture of 1/1) was kneaded with a 25 mmφ twin-screw extruder to prepare three types of masterbatches containing 3% by weight of fine particles 2, 4 or 8 and 2% by weight of an antistatic agent.

Then, using a polyethylene resin (same as above) mixed with 10% by weight of each master batch, three types of polyethylene films having a thickness of 30 μm were produced with a 30 mmφ inflation film forming machine. The appearance of each of the produced films was good, and no blocking was observed on any of the wound film rolls even after being left in an atmosphere of 23 ° C. × 65% RH for 2 weeks.

On the other hand, the film prepared and prepared in the same manner as above except that no fine particles were used was free of foreign matter and had a good appearance, but remarkable blocking was observed after standing as described above.

<Effects of the Invention> As is clear, in the present invention described above, the surface properties of the thermoplastic resin film, that is, the lubricity and the anti-blocking property, are not affected without adversely affecting the intrinsic properties of the thermoplastic resin film. There is an effect that it can be improved.

Claims (4)

(57) [Claims] (1) 0.005 to 5% by weight of the following spherical composite fine particles:
A thermoplastic resin film having improved lubricity and anti-blocking property, characterized by comprising: Spherical composite fine particles: spherical particles formed from a copolymer in which a polysiloxane block of the following (I) and a vinyl polymer block of the following (II) are cross-linked to each other using R ³ in the polysiloxane block as a linking hand. Composite fine particles,
And the polysiloxane block / the vinyl polymer block is 97/3 to 20/80 (weight ratio), and the average particle size is 0.05 to 5
μm, spherical composite fine particles having a standard deviation of particle size distribution of 1.0 to 2.5, and a ratio of major axis to minor axis of 1.0 to 1.2. (I): 99.9 to 0 mol% of one or more structural units represented by the general formula [R ¹ _a SiO _{(4-a) / 2} ] and the general formula [R ² _m R ³ _n SiO _{(4) -Mn) / 2} ] is a polysiloxane block composed of 0.1 to 100 mol% of structural units represented by the formula (1) and wherein a is 1 or less and / or m + n is 1. A polysiloxane block containing 15 mol% or more of structural units in total. [However, a is an integer of 0 to 3. m is an integer of 0 to 2, n is 1
An integer satisfying 1 ≦ m + n ≦ 3.
R ¹ and R ² are the same or different unsubstituted or substituted non-radical polymerizable hydrocarbon groups having a carbon atom directly bonded to a silicon atom. R ³ is a group represented by AB. A is an alkylene group having 2 or 3 carbon atoms directly bonded to a silicon atom.
B is a direct bond or One or more selected from (b is an integer of 0 to 3). ｝. (II): a vinyl polymer block obtained by polymerizing one or more kinds of radically polymerizable vinyl monomers containing an ethylenically unsaturated group. 2. The vinyl polymer block in the copolymer forming the spherical composite fine particles is an aromatic vinyl polymer block or an aliphatic vinyl polymer block obtained by polymerizing an alkyl ester of methacrylic acid or acrylic acid. The thermoplastic resin film according to claim 1, wherein the thermoplastic resin film has improved lubrication and anti-blocking properties. 3. The spherical composite fine particles have an average particle size of 0.1 to 3 μm.
The thermoplastic resin film according to claim 1 or 2, wherein the m and the standard deviation of the particle size distribution are 1.0 to 2.0, and the ratio of the major axis to the minor axis is 1.0 to 1.1. . 4. The thermoplastic resin film according to claim 1, wherein the thermoplastic resin film is formed from a resin composition containing a linear aromatic polyester as a main component and has improved lubricity and antiblocking property.