JPH11166059A - Anti-clouding molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-clouding molding exhibiting electrostatic properties and anti-clouding properties from just after molding and having stable antistatic properties and anti-clouding properties for a long period of time. SOLUTION: In this anti-clouding molding, the ratio of oxygen number to carbon number (O/C) in the surface of (A) a thermoplastic resin is >=(10/100) and (B) an anti-clouding agent disperses in a state satisfying the relations of an average particle diameter of 0.05-0.5 μm, the ratio of an average particle diameter in long axis (Lw) to an average particle diameter in short axis (Lh) of the dispersed particles (Lw/Lh) is <=3.0 and the average distance between center of gravity of the dispersed particles with each other is <=1.5 μm within the range at least 5 μm thickness from the surface of the molded material. Preferably, the molding is used as an anti-clouding film, especially an agricultural film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifogging molded article, and more particularly, to an antifogging article which exhibits antifogging performance immediately after molding and has stable antifogging performance for a long period of time. To conductive films, especially agricultural films.

[0002] Thermoplastic resins are excellent in moldability, chemical resistance, mechanical properties, etc., and are therefore processed into injection molded articles, hollow molded articles, films, sheets, fibers and the like, and used for various purposes. I have. However, since a thermoplastic resin generally has a large contact angle with water, fine water droplets are easily formed and water is easily repelled.

[0003] Therefore, in order to improve the suitability of use, when the molded article is easily wetted with water, or when used as a film or molded article for agriculture or food, the thermoplastic resin has an antifogging agent such as a surfactant. The fact is that the agent is blended. Surfactants used in such a thermoplastic resin include those that exhibit antistatic performance and antifogging performance immediately after molding, and those that exhibit these performances over a long period of time. I have.

[0004]

Among them, those exhibiting antistatic performance and antifogging performance over a long period of time are:
There is a problem that the initial performance is often difficult to obtain, and if a large amount of a surfactant having a rapid effect is used to solve this problem, the product becomes sticky during long-term use,
It is likely to cause product defects such as whitening. For this reason, conventionally, an appropriate combination of a surfactant having an excellent antistatic effect and an anti-fogging agent having an excellent effect and a surfactant having an antistatic agent and an anti-fogging agent having a long-lasting effect is used. And deal with it.

However, even when a plurality of antifogging agents are used in combination as described above, it is difficult to exhibit a long-lasting performance because the bleeding property of the surfactant is unstable. In particular, it is extremely difficult to obtain a film that can stably maintain the anti-fog performance for a long period of time outdoors, where the film is exposed to the wind and rain and the temperature fluctuates greatly.

The inventors of the present invention have conducted intensive studies in view of such prior art, and as a result, by dispersing an anti-fogging agent with a specific particle size in a thermoplastic resin molded article, an excellent anti-fogging effect has been obtained immediately after molding. The present inventors have found that they exhibit performance and have stable performance over a long period of time, and have completed the present invention.

The object of the present invention is to provide a thermoplastic resin, especially a polyolefin-based molded article, which exhibits antifogging performance immediately after molding and is stable for a long period of time in view of the above situation. It is intended to obtain a polyolefin molded article having performance.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been proposed in order to achieve the above-mentioned object, and it is an object of the present invention to provide an antifogging agent having a specific dispersion state in a thickness of at least 5 μm from the surface of a molded article. There is an important feature to make exist.

That is, according to the present invention, a thermoplastic resin
(A) The ratio of the number of oxygen atoms to the number of carbon atoms (O
/ C) is not less than 10/100 and at least 5 μm in thickness from the surface of the molded product, the antifogging agent (B) is
The average particle size is 0.05 to 0.5 μm; the ratio of the average value (Lw) of the particle size in the major axis direction of the dispersed particles to the average value (Lh) of the particle size in the minor axis direction, Lw / Lh is 3. 0 or less; and the average value of the distance between the centers of gravity of the dispersed particles is 1.5 μm or less.

According to the present invention, the antifogging agent (B)
However, the present invention provides the above antifogging molded article containing, in the molecule, at least one of the polar groups represented by the following (I) to (V). -(R ¹ -O) _n -R ² (I) (wherein R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, 1 to 22 carbon atoms) Represents a linear or branched alkyl group.
Represents an integer of 1 to 30. _{) -OH (II) -SO 3 X} (III) ( wherein, X represents a hydrogen atom, Na, K, representing a _{^{Li) -N + R 3 X -}} (IV) ( wherein three of R respectively also same thing may be different, having 1 to hydrogen atom or a C represent 3 alkyl group, X is Cl, represents Br or _{^{I) -N + R 2 COO -}} (V) ( wherein, 2 pieces R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

According to the present invention, the antifogging agent (B) has a weight average molecular weight of 100 to 8,000, preferably 1 as measured by gel permeation chromatography.
In the range of 00 to 5,000, wherein the thermoplastic resin
The absolute value (dX) of the difference between the value of the solubility parameter (Xa) of (A) and the value of the solubility parameter (Xb) of the antifogging agent (B).
= | Xa-Xb |) is 0 to 1 (cal / ml) ^1/2
Is provided.

Further, according to the present invention, the thermoplastic resin
(A) is a polyolefin, and the value of the solubility parameter of the antifogging agent (B) is 7 to 9 (cal / ml) ^1/2
Is provided.

According to the present invention, the antifogging agent (B)
Is a carboxylic acid-containing polyolefin wax (C), or a higher fatty acid having 16 or more carbon atoms and a derivative thereof (D)
And a polyoxyalkylene-containing compound (E) represented by the following formula VI: X- (R ¹ -O) _n -R ² (VI) (where X represents OH or NH ₂ , and R ¹ has ¹ carbon atom)
Represents a linear or branched alkyl group of
R ² represents a linear or branched alkyl group having 1 to 22 carbon atoms. n represents an integer of 1 to 30)

Further, according to the present invention, there is provided the above antifogging molded article, wherein the molded article is a film.

Further, according to the present invention, there is provided the above antifogging molded article, wherein the film is an agricultural film.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The antifogging molded article according to the present invention will be described below.
And the molded product will be specifically described.

<Anti-fogging molded article> The anti-fogging molded article of the present invention comprises a thermoplastic resin (A) having the number of oxygen atoms on the molded article surface
When the ratio (O / C) to the number of carbon atoms is 10/100 or more and the thickness is at least 5 μm from the surface of the molded product, the antifogging agent (B) has an average particle diameter of 0.05 to 0. 0.5 μm, preferably 0.05 to 0.3 μm; the ratio of the average value (Lw) of the particle diameter in the long axis direction to the average value (Lh) of the particle diameter in the short axis direction of the dispersed particles, and Lw / Lh is 3 .0
Or less, preferably 2.5 or less; and the average value of the distance between the centers of gravity of the dispersed particles is 1.5 μm or less, preferably 1.0 μm or less.
An important feature is that the particles are dispersed in a state satisfying the following relationship: μm or less.

The number of oxygen atoms and the number of carbon atoms on the surface of the compact are
It is measured using X-ray photoelectron spectroscopy, and the ratio (O / C) of the number of oxygen atoms to the number of carbon atoms on the surface of the molded product is 1
When it is 0/100 or more, preferably 15/100 or more, both the initial antifogging property and the antifogging durability become excellent, as is clear from the examples described later.

The antifogging molded article of the present invention is characterized in that

As long as the requirements described above are satisfied, it can be obtained by various known molding methods such as an injection molding method, an extrusion molding method and a stretch molding method. Specifically, for example, it can be manufactured by extruding a molten thermoplastic resin composition from a T-die using a single screw extruder, a kneading extruder, a ram extruder, a gear extruder, or the like. As the molding conditions, conventionally known conditions can also be adopted. The film may be stretched, and the stretched film is formed by using a sheet or film made of the thermoplastic resin composition as described above, using a conventionally known stretching apparatus, and using a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), It can be manufactured by a biaxial stretching method, a uniaxial stretching method, or the like. Further, the film may be a blown film.

The film according to the present invention may be a multilayer film, for example, a three-layer laminated film comprising an outer layer, an intermediate layer and an inner layer, wherein at least one layer is formed from the thermoplastic resin composition. Is mentioned. The film according to the present invention has antistatic performance and antifogging performance immediately after molding, and has stable antistatic performance and antifogging performance over a long period of time.

Such a film is particularly suitable as an agricultural film, and has excellent antifogging durability, dustproofness and toughness as compared with conventional agricultural films. In addition, this film has the advantages that it is lightweight and has a low amount of low molecular weight components in the polymer used, so that it has little stickiness, is excellent in workability in spreading, and has little fusion between films at high temperatures. Since this film has the above-mentioned effects, it can be spread over agricultural and horticultural facilities such as houses and tunnels and used for a long time in cultivation of useful crops.

<(A) Thermoplastic Resin> As the thermoplastic resin used in the present invention, various known resins can be used. Particularly, polyethylene, polypropylene, poly-1-butene, polymethylpentene, polymethyl Olefin homopolymer such as butene, ethylene-vinyl acetate copolymer,
Polyolefins such as olefin copolymers such as ethylene-α-olefin random copolymer and propylene-ethylene random copolymer are preferable, and among them, polyethylene, polypropylene and ethylene-α-olefin random copolymer are preferable. When the polyolefin is a polyolefin obtained from an olefin having 3 or more carbon atoms, it may be an isotactic polymer or a syndiotactic polymer. Among these, an ethylene homopolymer or an ethylene / α-olefin random copolymer is particularly preferred.

The ethylene homopolymer or ethylene / α-olefin random copolymer suitable for the present invention has a density in the range of 0.880 to 0.960 g / cm ³ and a melt flow rate (MFR; ASTM D).
1238-65T, 190 ° C, load 2.16 kg)
It is desirable to be in the range of 0.01 to 100 g / 10 min.

These polyolefins can be produced by a known method such as a high-pressure radical polymerization, a medium / low pressure polymerization method carried out in the presence of a transition metal compound catalyst such as a Ziegler-Natta type catalyst or a metallocene catalyst. Especially,
When used as an agricultural film, the density obtained by the medium / low pressure polymerization method is 0.880 to 0.935 g / cm.
³ , ethylene having an MFR of 0.1 to 20 g / 10 min.
α-olefin copolymer or such ethylene-α-
The density obtained by the olefin copolymer and the high-pressure radical polymerization is 0.910 to 0.935 g / cm ³ , and the MFR is 0.
A composition with a high-pressure low-density polyethylene of 1 to 20 g / 10 min is preferable in view of moldability, light transmittance, strength, and weather resistance. The above thermoplastic resins can be used alone or in combination of two or more.

<(B) Antifogging agent> The antifogging agent used in the present invention has a ratio (O / C) of the number of oxygen atoms to the number of carbon atoms on the surface of the thermoplastic resin (A) molded product of 10/100. The compound is not particularly limited as long as it satisfies the above requirements, but is preferably a compound containing at least one of the polar groups represented by the following (I) to (V) in the molecule. -(R ¹ -O) _n -R ² (I) (wherein R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, 1 to 22 carbon atoms) Represents a linear or branched alkyl group.
Represents an integer of 1 to 30. _{) -OH (II) -SO 3 X} (III) ( wherein, X represents a hydrogen atom, Na, K, and Li) -N ⁺ R ₃ X ^- in (IV) (wherein, R represents a hydrogen atom, and represents an alkyl group having 1 to 3 carbon atoms, X is Cl, Br, a representative) -N ⁺ R ₂ COO I ^- in (V) (wherein, R represents a hydrogen atom, and the 3 alkyl groups having 1 to carbon atoms Represent)

The weight average molecular weight of the antifogging agent measured by GPC is usually in the range of 100 to 8,000, preferably 100 to 5,000, more preferably 200 to 4,000. Those having less than 1,000 are preferable from the viewpoint of improving the antifogging property. further,
The value of the solubility parameter of the thermoplastic resin (A) (X
The absolute value (dX = | Xa-Xb |) of the difference between the solubility parameter (Xb) of the antifogging agent (B) and a) shows good compatibility, and the dispersion state is good. , 0 or 1
(Cal / ml) ^1/2 , especially 0.2 to 0.6
(Cal / ml) ^1/2 is preferred. When the thermoplastic resin (A) is a polyolefin, the solubility parameter (Xj) of the antifogging agent (B) is 7 to 9 (cal / m
l) It is preferable that the ratio is ^1/2 because the compatibility with the thermoplastic resin becomes good.

Specific examples of the antifogging agent used in the present invention include surfactants (B-1) such as ionic surfactants and nonionic surfactants, and modified polyolefins (B-2). Can be An example will be described below.

<(B-1) Surfactant> Examples of the surfactant which can be used in the present invention include aliphatic sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, and higher alcohols. Phosphoric acid ester salts, higher alcohol ethylene oxide adduct phosphoric acid ester salts, quaternary ammonium salt type cationic surfactants, ionic surfactants such as betaine type amphoteric surfactants, glycerin monofatty acid esters, glycerin difatty acid esters , Glycerin trifatty acid ester,
Diglycerin fatty acid ester, polyethylene glycol fatty acid ester, higher alcohol ethylene oxide adduct, polyhydric alcohol fatty acid ester, N, N-bis (2-hydroxyethyl) aliphatic amine, N, N-bis (2-hydroxyisopropyl) fat Group amine, N, N
-Bis (2-hydroxyethyl) aliphatic amide, N, N
Non-ionic surfactants such as -bis (2-hydroxyisopropyl) aliphatic amide.

Specifically, aliphatic sulfonates such as sodium lauryl sulfonate; higher alcohol sulfates such as sodium lauryl alcohol sulfate; sodium salt of lauryl alcohol EO 4-mol adduct sulfate sodium salt (EO = ethylene oxide) ) Or other higher alcohol ethylene oxide adduct sulfates; octyl alcohol phosphate Na, lauryl alcohol phosphate Na, cetyl alcohol phosphate N
a higher alcohol phosphate ester salts such as a salt, stearyl alcohol phosphate sodium salt, oleyl alcohol phosphate sodium salt; octyl alcohol EO 4-mol adduct phosphate ester sodium salt, lauryl alcohol E
O4 mol adduct phosphate Na salt, cetyl alcohol EO 4 mol adduct phosphate Na salt, stearyl alcohol EO 4 mol adduct phosphate Na salt, oleyl alcohol EO 4 mol adduct phosphate Na
Higher alcohol ethylene oxide adduct phosphates such as salts; quaternary ammonium salt type cationic surfactants such as lauryl trimethyl ammonium methosulfate; betaine type amphoteric surfactants such as lauryl dimethyl betaine; glycerin monolaurate, glycerin Monomyristylate, glycerin monopalmitate,
Glycerin monofatty acid esters such as glycerin monostearate, glycerin monobehenate and glycerin monooleate; glycerin such as glycerin dilaurate, glycerin dimyristylate, glycerin dipalmitate, glycerin distearate, glycerin dibehenate and glycerindiolate Difatty acid ester; glycerin trilaurate, glycerin trimyristylate,
Glycerin trifatty acid esters such as glycerin tripalmitate, glycerin tristearate, glycerin tribehenate, glycerin triolate; diglycerin monolaurate, diglycerin monomyristylate,
Diglycerin fatty acid esters such as diglycerin monopalmitate, diglycerin monostearate, diglycerin behenate, and diglycerin monooleate; polyethylene such as polyethylene glycol 200 monolaurate, polyethylene glycol 200 monostearate, and polyethylene glycol 200 monooleate Glycol fatty acid ester; lauryl alcohol EO 2 mol adduct, lauryl alcohol EO 4 mol adduct, lauryl alcohol EO 6 mol adduct, lauryl alcohol EO1
Higher alcohol ethylene oxide adducts such as 0 mol adduct, 4 mol adduct of nonylphenol EO, and 10 mol adduct of nonylphenol EO;

Higher fatty acids and their derivatives (D) and formula VI
X- (R ¹ -O) _n -R ² (VI) (wherein X represents OH or NH ₂ , and R ¹ represents the number of carbon atoms) 1
Represents a linear or branched alkyl group of
R ² is a linear or branched alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 to 30)

Sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, mono (di or tri) stearyl citrate, pentaerythritol fatty acid ester, trimethylolpropane fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan Polyhydric alcohol fatty acid esters such as fatty acid esters, polyethylene glycol fatty acid esters, and polypropylene glycol fatty acid esters; N, N-bis (2-hydroxyethyl) laurylamine, N, N-bis (2-hydroxyethyl) myristylamine; N-bis (2-hydroxyethyl) palmitylamine, N, N-bis (2-hydroxyethyl) stearylamine, N, N-bis (2-
N, N-bis (2-hydroxyethyl) aliphatic amines such as hydroxyethyl) oleylamine; N, N-bis (2-hydroxyisopropyl) laurylamine;
N-bis (2-hydroxyisopropyl) myristylamine, N, N-bis (2-hydroxyisopropyl) palmitylamine, N, N-bis (2-hydroxyisopropyl) stearylamine, N, N-bis (2-hydroxy N, N-bis (2-hydroxyisopropyl) aliphatic amines such as isopropyl) oleylamine; N, N
-Bis (2-hydroxyethyl) laurylamide, N,
N-bis (2-hydroxyethyl) myristylamide,
N, N-bis (2-hydroxyethyl) palmitylamide, N, N-bis (2-hydroxyethyl) stearylamide, N, N-bis (2-hydroxyethyl) behenylamide, N, N-bis (2 N, N-bis (2-hydroxyethyl) aliphatic amides such as -hydroxyethyl) oleylamide; N, N-bis (2-hydroxyisopropyl) laurylamide, N, N-bis (2-hydroxyisopropyl) myristylamide , N, N-bis (2-hydroxyisopropyl) palmitylamide,
N, N-bis (2-hydroxyisopropyl) aliphatic amides such as N, N-bis (2-hydroxyisopropyl) stearylamide and N, N-bis (2-hydroxyisopropyl) oleylamide.

Further, mono- or diesters of the above-mentioned N, N-bis (2-hydroxyethyl) aliphatic amine with fatty acids such as lauric acid and stearic acid may be mentioned. Further, mineral oil, lauryl alcohol, diethylene glycol monolaurate, polyoxyethylene glycol fatty acid alcohol ether, polyoxyethylene alkylphenyl ether, polyoxypropylene-polyoxyethylene block polymer, polyethylene glycol, polypropylene glycol and the like can be mentioned.

Among these surfactants, the above-mentioned surfactants are formed by a usual molding method.

The use of a reaction product of a higher fatty acid (D) and a derivative thereof with the polyoxyalkylene-containing compound (E) represented by the above formula VI is advantageous in that an antifogging molded article satisfying the requirements of the above is obtained. preferable.

<(B-2) Modified Polyolefin> The modified polyolefin used in the present invention is an α-olefin having 2 to 8 carbon atoms.
And at least one selected from olefins as a main component, and a polar group represented by the above formulas I to V. As a method for producing such a modified polyolefin, a conventionally known method can be used.

Specifically, (1) α-C 2 -C 8
A method of reacting an olefin homopolymer or a copolymer thereof with an unsaturated compound having a polar group represented by the above formulas I to V in the presence or absence of a radical initiator, (2) carboxylic acid Containing polyolefin and the above formula
A method of reacting a polar group represented by I to V with a monomer having a polar group reactive with a carboxylic acid is exemplified.

Among these, the method of reacting a carboxylic acid-containing polyolefin with a monomer having a polar group represented by the above formulas I to V and a polar group reactive with carboxylic acid is preferred. Further, in the present invention, it is preferable to use a reaction product of the carboxylic acid-containing polyolefin wax (C) and the polyoxyalkylene-containing compound (E) represented by the above formula VI.

The solubility parameter is determined from the molecular volume (ΔV _i ) and the evaporation energy (Δe _i ) of each functional group constituting the molecule by the formula Xb = (ΣΔe _i / ΣΔV _i ) ^1/2 . The antifogging agent (B) preferably has a solubility parameter (Xb) of 7 to 9 (cal / ml) ^1/2 . The details of this calculation method are described in “Coating Technique”, June 1990, page 161.

<(C) Carboxylic acid-containing polyolefin wax> The carboxylic acid-containing polyolefin wax used in the present invention includes (1) a homopolymer wax of an α-olefin having 2 to 8 carbon atoms or two or more α-olefins. Or a method of (2) radically polymerizing an α-olefin having 2 to 8 carbon atoms and an unsaturated carboxylic acid under high pressure under a high pressure.

The unsaturated carboxylic acids used herein include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [ 2,2,1] Hept-2-
Unsaturated carboxylic acids such as ene-5,6-dicarboxylic acid or derivatives thereof (acid anhydride, acid halide, amide,
Imide, ester, etc.).

Examples of the derivative include maleenyl chloride, melenimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tettahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6- Dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citrate, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2
Dimethyl ene-5,6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate,
Examples include aminoethyl methacrylate and aminopropyl methacrylate. Among these, (meta)
Acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate,
Aminopropyl methacrylate is preferred.

<Higher Fatty Acids and Derivatives Thereof> Specific examples of the higher fatty acids used in the present invention include lauric acid,
Palmitic acid, stearic acid, behenic acid, montanic acid and the like. Among them, higher fatty acids having 16 or more carbon atoms are preferable, and those obtained by oxidizing or hydrolyzing natural wax are more preferable.

The natural wax used in the present invention includes plants,
A wax secreted by animals and extracted from minerals. It is an esterified product of higher fatty acids and higher alcohols and is a solid compound at room temperature. Specific examples of the vegetable wax used in the present invention, candelilla wax,
Carnauba wax, rice wax, wood wax, jojoba oil and the like. Specific examples of animal waxes include beeswax, lanolin (wool fat), and whale wax. Further, a specific example of the mineral wax is montan wax.

In the present invention, it is desirable to use a higher fatty acid obtained by oxidizing or hydrolyzing the natural wax. As a method of oxidizing or hydrolyzing the natural wax, a conventionally known method can be used as it is, for example, a method of oxidizing the natural wax with chromic acid such as chromium sulfate, or hydrolyzing in the presence of an acid catalyst. Method and the like. The higher fatty acids obtained by such a method may be used alone or in combination of two or more. Among these higher fatty acids, it is preferable to use montanic acid wax obtained by oxidizing montan wax with chromic acid because of its excellent quality such as hue and hardness.

<(E) Polyoxyalkylene-containing compound>
Polyoxyalkylene-containing compound (E) used in the present invention
Are amine and alcohol compounds containing a polyoxyalkylene moiety of formula VI. Specific examples of these compounds include poly (3 mol) oxyethylene lauryl ether, poly (4 mol) oxyethylene lauryl ether, poly (5 mol) oxyethylene lauryl ether, poly (6 mol) oxyethylene lauryl ether Poly (9 mol) oxyethylene lauryl ether, poly (14 mol) oxyethylene lauryl ether, poly (30 mol) oxyethylene lauryl ether; poly (3 mol) oxyethylene methyl ether, poly (4 mol) oxyethylene methyl ether , Poly (5
Mol) oxyethylene methyl ether, poly (6 mol)
Oxyethylene methyl ether, poly (30 mol) oxyethylene methyl ether; poly (3 mol) oxyethylene butyl ether, poly (5 mol) oxyethylene butyl ether, poly (14 mol) oxyethylene butyl ether, poly (30 mol) oxyethylene butyl ether Poly (5 mol) oxyethylene nonyl phenyl ether, poly (5 mol) oxyethylene nonyl phenyl ether, poly (5 mol) oxyethylene nonyl phenyl ether; poly (5 mol) oxyethylene phenyl ether, poly (14 mol) oxy Ethylene phenyl ether, poly (30 mol) oxyethylene phenyl ether; poly (5 mol) oxypropylene lauryl ether, poly (30 mol) oxypropylene lauryl ether, poly (5 mol) Carboxymethyl propylene methyl ether,
Poly (30 mol) oxypropylene methyl ether; poly (2 mol) oxypropylene-poly (5 mol) oxyethylene lauryl ether; amino-poly (5 mol) oxyethylene methyl ether, amino-poly (14 mol) oxyethylene methyl Ether, amino-poly (3
0 mol) oxyethylene methyl ether; amino-poly (2 mol) oxypropylene-poly (5 mol) oxyethylene methyl ether; polyethylene glycol, polypropylene glycol, polybutylene glycol, poly (oxyethylene) (oxypropylene), polyoxy And ethylenediamine. Among these,
In particular, poly (3 mol) oxyethylene methyl ether, poly (4 mol) oxyethylene methyl ether, poly (5
Mol) oxyethylene methyl ether, poly (6 mol)
Oxyethylene methyl ether, poly (3 mol) oxyethylene lauryl ether, poly (4 mol) oxyethylene lauryl ether, poly (5 mol) oxyethylene lauryl ether, poly (6 mol) oxyethylene lauryl ether, amino-poly (5 (Mol) oxyethylene methyl ether, and polyethylene glycol and polyoxyethylene diamine having a molecular weight of usually 100 to 5,000, preferably 100 to 3,000, more preferably 100 to 1,000.

Even when the above-mentioned surfactant (B-1) or modified polyolefin (B-2) is used, when the molded article is obtained by mixing with the thermoplastic resin (A).

If the requirements of the item are not satisfied, the antistatic and antifogging properties are not exhibited immediately after molding,
Not having stable performance for a long time,
The object of the present invention cannot be achieved.

In the present invention, the thermoplastic resin composition, which is the material of the antifogging molded article, may contain, if necessary, a phase such as a higher fatty acid metal salt, a polyolefin wax, a hydrogenated petroleum resin, or an antistatic agent other than the above. A solubilizer may be used. In addition, heat stabilizers, weather stabilizers, hindered amine stabilizers, nucleating agents, metal deactivators, lubricants, anti-blocking agents, slip agents, warming agents, anti-fog agents, release agents, inorganic fillers, pigment dispersions Various compounding agents such as agents, pigments, dyes, and cross-linking agents may be compounded within a range that does not impair the object of the present invention.

<Heat Stabilizer> Examples of the heat stabilizer used in the present invention include a phenol stabilizer, a phosphorus stabilizer and a sulfur stabilizer.

<Phenol Stabilizer> As the phenol stabilizer, a phenol stabilizer conventionally used as a stabilizer is used without any particular limitation. The following compounds are used as specific phenolic stabilizers. 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4
-Ethylphenol, 2,6-dicyclohexyl-4-
Methylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n
-Octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-
4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, dl-α-tocopherol, t-butylhydroquinone, 2,2′-methylenebis (4-methyl-6 t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2
-Thiobis (4-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-
Methylcyclohexyl) -p-cresol], 2,2 ′
-Ethylidenebis (4,6-di-t-butylphenol), 2,2′-butylidenebis (2-t-butyl-4)
-Methylphenol), 2-t-butyl-6- (3-t
-Butyl-2-hydroxy-5-methylbenzyl) -4
-Methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl]
-4,6-di-t-pentylphenyl acrylate,
1,1,3-tris (2-methyl-4-hydroxy-5
-T-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5 -Di-t-butyl-4
-Hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate], N, N'-
Hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris (2,6-dimethyl-3- Hydroxy-
4-t-butylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2,
6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-
Hydroxy-3,5-di-t-butylanilino) -1,
3,5-triazine, tetrakis [methylene-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, 2,2'-methylenebis (4
-Methyl-6-t-butylphenol) terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, 3,9-bis [1,1-dimethyl-2-Δβ
-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,1
0-tetraoxaspiro [5,5] undecane, 2,2
-Bis [4- (2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Stearyl propionate and the like.

Of these, β- (3,5-di-t-
Stearyl butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-)
Hydroxybenzyl) isocyanurate, 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, dl-α-
Tocopherol, tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate,
Tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {β- (3
-T-butyl-4-hydroxy-5-methylphenyl)
Propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred.

Commercial products can also be used as the phenolic stabilizer, for example, Irganox 1010 (Irganox).
nox1010, Ciba Geigy, trademark), Irganox 10
76 (Irganox1076, Ciba-Geigy, trademark), Irganox 1330 (Irganox1330, Ciba-Geigy, trademark), Irganox 3114 (Irganox3114, Ciba-Geigy, trademark), Irganox 3125 (Irganox3125)
Biba (Takeda Pharmaceutical Co., Ltd., trademark), Cyanox 1790 (Cyanox 1790, Cyanamid, trademark), Sumilizer GA-80 (Sumi
lizerGA-80, Sumitomo Chemical Co., Ltd., trade name), vitamin E (Eisai Co., Ltd.) and the like. These phenolic stabilizers can be used alone or in combination.

The amount of the phenolic stabilizer is 0.005 to 2 parts by weight per 100 parts by weight of the thermoplastic resin.
Preferably it is 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight. When the content of the phenolic stabilizer is within the above range with respect to 100 parts by weight of the thermoplastic resin, heat resistance, the effect of improving stability such as aging resistance is high, and the cost of the stabilizer is reduced. Inexpensive, and the properties of the thermoplastic resin, such as tensile strength, do not decrease.

<Phosphorus Stabilizer> As the phosphorus stabilizer,
A phosphorus-based stabilizer conventionally used as a stabilizer is used without any particular limitation. The following compounds are used as specific examples of the phosphorus-based stabilizer. Trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris (butoxyethyl) phosphite, Tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1,3
- tris (2-methyl -5-t-butyl-4-hydroxyphenyl) butane diphosphite, tetra (C ₁₂ to C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) −4
4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, tris (3,5-di-t-
Butyl-4-hydroxyphenyl) phosphite, tris (mono / di-mixed nonylphenyl) phosphite, hydrogenated-4,4′-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4 ′
-Butylidenebis (3-methyl-6-t-butylphenol)] • 1,6-hexanediol diphosphite;
Phenyl-4,4'-isopropylidenediphenol
Pentaerythritol diphosphite, Tris [4,
4'-isopropylidenebis (2-t-butylphenol)] phosphite, phenyl diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, tris (1,3-di-stearoyloxyisopropyl) phosphite, , 4'-Isopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-1
0-oxide, bis (2,4-di-t-butyl-6-
Methylphenyl) -ethyl phosphite, 2-[｛2
4,8,10-tetrakis (1,1-dimethylethyl)
Dibenzo (D, F) (1,3,2) -dioxaphosphen-6-yl {oxy] -N, N-bis [2-
[{2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo (D, F) (1,3,2) -dioxaphosphen-6-yl} oxy] ethyl] ethanamine and the like.

Further, bis (dialkylphenyl) pentaerythritol diphosphite ester is represented by the following general formula:
A spiro type represented by (VII) or a cage type represented by general formula (VIII) is also used. Usually, mixtures of both isomers are most often used for economic reasons arising from the process for producing such phosphite esters.

[0055]

Embedded image Here, R ¹ , R ² , and R ³ are hydrogen or carbon atom 1
To 9 alkyl groups, particularly a branched alkyl group, particularly a tert-butyl group, and the phenyl group is most preferably substituted at the 2, 4, and 6-positions.
Suitable phosphite esters are bis (2,4-di-t
-Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, etc.
In addition, a phosphonite having a structure in which carbon and phosphorus are directly bonded, for example, a compound such as tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite is also included.

As the phosphorus-based stabilizer, a commercially available product can be used. For example, Irgafos 168 (Irgafos 168) can be used.
, Ciba-Geigy, trademark), Irgafos 12 (Irgaf
os 12, Ciba-Geigy, trademark), Irgafoss 38 (I
rgafos 38, Ciba-Geigy, trademark), Mark 329K
(Mark 329K, Asahi Denka Co., Ltd., trademark), Mark PEP3
6 (Mark PEP36, Asahi Denka Co., Ltd., trademark), Mark PEP
-8 (Mark PEP-8, Asahi Denka Co., Ltd., trademark), Sands
tab P-EPQ (Clariant, trademark), Weston 618 (Weston 618, GE, trademark), Weston 619G (Weston 619G, GE, trademark), Weston-624 (Weston-624, GE, trademark) and the like. Can be These phosphorus-based stabilizers can be used alone or in combination.

The amount of the phosphorus stabilizer is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the thermoplastic resin. It is desirable to use parts by weight. When the content of the phosphorus-based stabilizer is within the above range with respect to 100 parts by weight of the thermoplastic resin, the effect of improving stability such as heat resistance and aging resistance is high, and the cost of the stabilizer is reduced. Inexpensive, and the properties of the thermoplastic resin, such as tensile strength, do not decrease.

<Sulfur Stabilizer> As the sulfur stabilizer, a sulfur stabilizer conventionally used as a stabilizer is used without any particular limitation. As specific examples of the sulfur-based stabilizer, the following compounds are used. Dialkylthiodipropionates such as dilauryl-, dimyristyl- and distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl- and stearyl- (eg glycerin, trimethylolethane, trimethylolpropane, pentane) Esters of erythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralauryl thiopropionate) and the like. More specifically, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodibutyrate and the like can be mentioned.

As the sulfur-based stabilizer, commercially available products can also be used. For example, DSTP (Yoshitomi) (Yoshitomi Pharmaceutical Co., Ltd., trademark), DLTP (Yoshitomi) (Yoshitomi Pharmaceutical Co., Ltd., trademark), DLTOIB (Yoshitomi Pharmaceutical Co., Ltd.,
Trademark), DMTP (Yoshitomi) (trademark of Yoshitomi Pharmaceutical Co., Ltd.), Seenox 412S (Shiraishi Calcium Co., Ltd.)
And Cyanox 1212 (Cyanamide Corporation, trademark). These sulfur-based stabilizers can be used alone or in combination.

The amount of the sulfur-based stabilizer is 0.005 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin.
Preferably it is 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight. When the content of the sulfur-based stabilizer is within the above range with respect to 100 parts by weight of the thermoplastic resin, the effect of improving stability such as heat resistance and aging resistance is high, and the cost of the stabilizer is reduced. Inexpensive, and the properties of the thermoplastic resin, such as tensile strength, do not decrease.

<Weather Resistance Stabilizer> As the weather resistance stabilizer used in the present invention, compounds conventionally used for improving weather resistance can be used without any particular limitation. Known weather resistance stabilizers, light stabilizers and ultraviolet light stabilizers can be used. An absorbent or the like can be used.
Specific examples of the weather resistance stabilizer include the following compounds. 2,4-dihydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone,
2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-4′-chlorobenzophenone, p-tert-butylphenyl salicylate, 2, 2'-dihydroxy-4,4'-dimethoxybenzophenone, ethyl-2-cyano-3,3-diphenylacrylate, 2-hydroxy-4-benzyloxybenzophenone, 2- (2'-hydroxy-3'-t
tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ',
5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-4′-tert-octylphenyl) benzotriazole, p-octylphenyl salicylate, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-n-
Octoxybenzophenone, 2- (2'-hydroxy-
4'-octoxyphenyl) benzotriazole, 2-
(3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-
3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2-ethyl-2'-ethoxy-5'-tert-butyl-N, N'-diphenyloxamide, 2-ethyl-2 '-Ethoxy-N, N'-diphenyloxamide, 2-hydroxy-4-dodecyloxybenzophenone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 3 , 5-di-tert-butyl-4-hydroxymyristylbenzoate, bis (2,2 ′,
6,6′-tetramethyl-4-piperidine) sebacate, [2,2′-thiobis (4-tert-octylphenolate)]-tert-butylaminonickel (I
I), bis (3,5-di-tert-butyl-4-hydroxybenzoylphosphonic acid monoethyl ester) nickel salt, bis (3,5-di-tert-butyl-4-hydroxybenzoylphosphonic acid monooctyl) Ester) nickel salt, 2,2′-thiobis (4,4′-alkylphenol) nickel (II) salt,
Dimethyl succinate [2- (4-hydroxy-2,
2,6,6-tetramethyl-1-piperidyl) ethanol] condensation polymer, poly [{6- (1,1,3,3-tetramethylbutyl) imino} -1,3,5-triazine-
2,4-diyl {4- (2,2,6,6-tetramethylpiperidyl) imino} hexamethylene], 4-benzoyloxy-2,2,6,6-tetramethylpiperidine,
Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1- [2- {3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionyloxydiethyl] -4- [3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionyloxy] -2,
2,6,6-tetramethylpiperidine, polymethyl-propyl-3-oxy- {1- (2,2,6,6-tetramethyl) piperidinyl} siloxane, N, N'-bis (3-aminopropyl) ethylenediamine -2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,
3,5-triazine, 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butyl-malonic acid (1,2,2,6,6-pentamethyl-4-piperidyl ), 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), [2,2'-thiobis (4-tert-octylphenolate)]-2 -Ethylhexylamine-nickel II, 3,3'-methylenebis (2-hydroxy-4-
Methoxybenzophenone), 2,4-dibenzoylresorcinol, 1,3-bis (4-benzoyl-3-hydroxyphenoxy) -2-propyl methacrylate, 8
-Acetyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 3-hydroxyphenylbenzoate, 2,4,5- Trihydroxybutyrophenone, 2
-Ethylhexyl-2-cyano-3,3-diphenylacrylate, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4 -Dione, 1,3-bis (4-benzoyl-3-hydroxyphenoxy) -2-
Propyl acrylate, 2- (4-octoxy-2-hydroxyphenyl) benzotriazole, phenyl salicylate, 2,2′-methylenebis (6-tert-butyl-4-methylphenol), bis (1,2,2,
6,6-pentamethyl-4-piperidyl) sebacate,
1,2,2,6,6-pentamethyl-4-piperidinemethyl methacrylate, 2,2,6,6-tetramethyl-
4-piperidine methyl methacrylate, octadecene
N- (2,2,6,6-tetramethylpiperidinyl)-
N-maleimido oxamide copolymer,

<Hindered amine stabilizer> As the hindered amine stabilizer, a compound having a structure in which all hydrogen bonded to carbons at the 2- and 6-positions of piperidine, which has been conventionally known, is substituted with a methyl group is particularly limited. It is used without being performed, and specifically, the following compounds are used. (1) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (2) dimethyl-1- (2- (2-succinate)
(Hydroxyethyl) -4-hydroxy-2,2,6,6
-Tetramethylpiperidine polycondensate, (3) poly {[6-
(1,1,3,3-tetramethylbutyl) imino-1,
3,5-Triazine-2--4-diyl] [(2,2
6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, (4) tetrakis (2,2,6)
6-tetramethyl-4-piperidyl) -1,2,3,4
-Butanetetracarboxylate, (5) 2,2,6,6
-Tetramethyl-4-piperidinyl benzoate, (6)
Bis- (1,2,6,6-pentamethyl-4-piperidinyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, (7) bis-
(N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, (8) 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpipe Radinone), (9) (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,3
4-butanetetracarboxylate, (10) (mixed 1,2,2,6,6-pentamethyl-4-piperidyl /
Tridecyl) -1,2,3,4-butanetetracarboxylate, (11) mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl- 3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4
-Butanetetracarboxylate, (12) mix {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3-9- [2,
[4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (13) N, N′-bis (3-aminopropyl) ethylenediamine-2 -4-bis [N-butyl-N
-(1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, (14) poly {[6-N-morpholyl-1,3 , 5-
Triazine-2-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)
Imino]}, (15) a condensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, (16) [N-
(2,2,6,6-tetramethyl-4-piperidyl)-
2-methyl-2- (2,2,6,6-tetramethyl-4
-Piperidyl) imino] propionamide and the like.

In particular, the above (1), (2), (3),
The compounds (4), (8), (10), (11), (14) and (15) are preferably used. These hindered amine-based stabilizers are used alone or in combination.

The amount of the hindered amine stabilizer is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight, per 100 parts by weight of the thermoplastic resin. Part. When the content of the hindered amine-based stabilizer is within the above range with respect to 100 parts by weight of the thermoplastic resin,
The effect of improving stability, such as heat resistance and aging resistance, is high, and the cost of stabilizers is kept low.
For example, the tensile strength does not decrease.

<Nucleating Agent> The nucleating agent used in the present invention includes:
Nucleating agents such as organic phosphoric acid nucleating agents, sorbitol nucleating agents, aromatic carboxylic acid nucleating agents, high melting point polymer nucleating agents, inorganic nucleating agents, and rosin acid nucleating agents, alone or in combination These can be used in combination.

<Organic phosphoric acid-based nucleating agent> Examples of the organic phosphoric acid-based nucleating agent include compounds represented by the following general formula (IX).

Embedded image (Wherein, R ¹ is oxygen, sulfur or C 1-10
Wherein R ² and R ³ are hydrogen or C 1
A to 10 hydrocarbon group, R ^2, R ³ may be heterologous be homologous, R ² to each other, even though a ring by bonding R ³ s or R ² and R ³ Good, M is 1
A trivalent metal atom, and n is an integer of 1 to 3. )

Specific examples of the compound represented by the general formula (IX) include sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate,
Sodium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-
2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium- 2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-
Methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-
t-butylphenyl) phosphate, calcium-bis [2,2′-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2
2'-thiobis (4-ethyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-
Thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2 '-Thiobis (4-
t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-t -Butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-
Bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2 2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], Sodium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-
t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-t-butyl-
2,2'-biphenyl) phosphate, calcium-
Bis [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl-
6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di- Ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-
Di-t-butylphenyl) phosphate, calcium-bis [2,2′-ethylidene-bis (4,6-di-t
-Butylphenyl) phosphate], magnesium-
Bis [2,2′-ethylidene-bis (4,6-di-t-
Butylphenyl) phosphate], barium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2′-methylene-bis (4, 6-di-t-butylphenyl) phosphate] and aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], and mixtures of two or more thereof. Examples can be given. Particularly, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

Preferred examples of the organic phosphoric acid-based nucleating agent include compounds represented by the following general formula (X).

Embedded image (Wherein, R ¹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, M is a monovalent to trivalent metal atom, and n is an integer of 1 to 3.)

Specific examples of the compound represented by the general formula (X) include sodium-bis (4-t-butylphenyl) phosphate, sodium-bis (4-methylphenyl) phosphate, and sodium-bis (4-methylphenyl) phosphate. (4-ethylphenyl) phosphate, sodium-bis (4-
i-propylphenyl) phosphate, sodium-
Bis (4-t-octylphenyl) phosphate, potassium-bis (4-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium-bis (4-t-butylphenyl) ) Phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4
(T-butylphenyl) phosphate and a mixture of two or more thereof. Particularly, sodium-bis (4-t-butylphenyl) phosphate is preferable.

<Sorbitol Nucleating Agent> Preferred sorbitol nucleating agents include compounds represented by the following formula (XI).

Embedded image (In the formula, each R ¹ is the same or different and is hydrogen, halogen such as chlorine, or a hydrocarbon group having 1 to 10 carbon atoms. M and n are each an integer of 0 to 5.)

Specific examples of the compound represented by the general formula (XI) include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, , 3-benzylidene-2,4
-P-ethylbenzylidene sorbitol, 1,3-p-
Methylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol, 1,
3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol , 1,3,
2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) ) Sorbitol, 1,3,2,4-di (ps-butylbenzylidene) sorbitol,
3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (2 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-
Methoxybenzylidene) sorbitol, 1,3,2,4
-Di (p-ethoxybenzylidene) sorbitol, 1,
3-benzylidene-2-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4
-Benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene -2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-
Chlorbenzylidene sorbitol and 1,3,2,4
-Di (p-chlorobenzylidene) sorbitol and a mixture of two or more of these.
2,4-dibenzylidene sorbitol, 1,3,2,4
-Di (p-methylbenzylidene) sorbitol, 1,
3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol And mixtures of two or more thereof.

Preferred sorbitol nucleating agents include compounds represented by the following formula (XII).

Embedded image (In the formula, each R ¹ is the same or different and is an alkyl group having 1 or 2 carbon atoms.)

<Aromatic carboxylic acid-based nucleating agent> Preferred examples of the aromatic carboxylic acid-based nucleating agent include aluminum hydroxydipara-t-butylbenzoate represented by the following general formula (XIII).

Embedded image

Other examples of the nucleating agent include a high-melting polymer, other metal salts of aromatic carboxylic acids and aliphatic carboxylic acids, and inorganic compounds. Examples of the high melting point polymer include polyvinylcycloalkanes such as polyvinylcyclohexane and polyvinylcyclopentane, poly3-methylpentene-1, poly3-methylbutene-1, and polyalkenylsilane. Examples of the metal salt include aluminum benzoate, p
-T-butyl benzoic acid aluminum salt, sodium adipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate and the like. Examples of the inorganic compound include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, and sulfuric acid. Examples include barium, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, and the like. In addition, brominated biphenyl ether, cyclic triethylene glycol terephthalate, and the like can also be used.

<Rosinic Acid Nucleating Agent> In the present invention, a well-known rosin nucleating agent can be used. Examples of the rosin acid-based nucleating agent include rosin acid partial metal salts, such as rosin acid partial sodium salt, rosin acid partial potassium salt, and rosin acid partial magnesium salt. As the rosin acid-based nucleating agent, at least one kind of rosin acid partial metal salt selected from natural rosin, modified rosin and purified products thereof is preferable, and the rosin acid partial metal salt is dehydroabietic acid, dihydroabietic acid, dihydropimaric acid And at least one partial metal salt of rosin acid selected from these derivatives.
Particularly preferred is at least one kind of rosin acid partial metal salt selected from the rosin acid partial metal salt represented by (XIVa) and the rosin acid partial metal salt represented by the following general formula (XIVb). In the following general formulas (XIVa) and (XIVb), R ¹ is preferably an isopropyl group, and R ² and R ³ are preferably methyl groups.

[0076]

Embedded image (In the formula, R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.)

In this specification, the rosin acid partial metal salt is a reaction product of rosin acid and a metal compound, and is a mixture of a rosin acid metal salt and unreacted rosin acid and unreacted rosin acid. Both metal salts of rosin acid not containing are meant.

Examples of the metal compound which forms a metal salt by reacting with rosin acid include compounds having a metal element such as sodium, potassium and magnesium and forming a salt with the rosin acid. Metal chlorides, nitrates, acetates, sulfates, carbonates, oxides, hydroxides and the like can be mentioned.

The rosin acids include natural rosins such as gum rosin, tall oil rosin, and wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, α,
Various modified rosins such as β-ethylenically unsaturated carboxylic acid modified rosin; purified products of the natural rosin, purified products of the modified rosin, and the like.

The natural rosin includes resin acids such as pimaric acid, sandaracopimaric acid, parastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid and tetrahydroabietic acid. , Usually a plurality of types.

The unsaturated carboxylic acid used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin is, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid. , Acrylic acid, methacrylic acid and the like.

Among the above rosin acids, disproportionated rosin,
It is preferably at least one rosin acid selected from hydrogenated rosin and dehydrogenated rosin, and at least one rosin acid selected from dehydroabietic acid, dihydroabietic acid, dihydropimaric acid and derivatives thereof. More preferred.

The partial metal salt of rosin acid includes the partial sodium salt of rosin acid, the partial potassium salt of rosin acid and the partial magnesium salt of rosin acid.

In the present invention, the rosin acid has the general formula (X
It is particularly preferable to use a compound [compound (XIVa)] represented by IVa) or a compound [compound (XIVb)] represented by the above general formula (XIVb). General formula (XIVa) and general formula (XIVb)
Wherein R ¹ , R ² and R ³ may be the same or different and are a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl.
Examples thereof include an alkyl group having 1 to 8 carbon atoms such as butyl, tert-butyl, pentyl, heptyl and octyl, and these groups include a hydroxyl group, a carboxyl group,
It may have a substituent such as an alkoxy group and a halogen.

Specific examples of the cycloalkyl group include cycloalkyl groups having 5 to 8 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl.
These groups may have a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group, and a halogen.

The aryl group includes an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. These groups are substituted with a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group, and a halogen. May be provided.

Compound (XIVa) and compound (XIVa)
In b), a compound in which R ¹ , R ² and R ³ are each the same or different alkyl groups is preferable, and a compound in which R ¹ is an i-propyl group and R ² and R ³ are methyl groups is preferred. More preferred. The partial metal salt of such a compound is particularly excellent in improving the crystallization speed of the crystalline resin.

Specific examples of the compound (XIVa) include dehydroabietic acid, and specific examples of the compound represented by the compound (XIVb) include dihydroabietic acid. Such compound (XIVa) and compound (XIV
In b), for example, dehydroabietic acid represented by the formula (XIVa) is obtained by disproportionating or dehydrogenating natural rosin such as gum rosin, tall oil rosin, wood rosin, and then purifying.

Examples of the metal salt of the compound (XIVa) include a compound [compound (XVa)] represented by the following formula (XVa). Examples of the metal salt of the compound (XIVa) include the following formula:
And a compound represented by the formula (XVb) [compound (XVb)].

Embedded image

In the general formulas (XVa) and (XVb),
¹ , R ² and R ³ are those represented by the general formula (XIVa) and the general formula
The same as (XIVb). M is a monovalent to trivalent metal ion, specifically, lithium, sodium, potassium,
Monovalent metal ions such as rubidium and cesium; divalent metal ions such as beryllium, magnesium, calcium, strontium, barium and zinc; and trivalent metal ions such as aluminum. Among these, a monovalent or divalent metal ion is preferable, and a sodium ion, a potassium ion, and a magnesium ion are more preferable. n is the same integer as the valence of the metal ion M, and is an integer of 1 to 3.

Among the compounds (XVa) and (XVb), compounds wherein R ¹ , R ² and R ³ are the same or different alkyl groups, or a compound wherein M is a monovalent or divalent metal ion And R ¹ is i-
A compound in which R ² and R ³ are a methyl group, or a compound in which M is a sodium ion, a potassium ion or a magnesium ion, R ¹ is an i-propyl group, and R ² and R ³ Is a methyl group, and M is a sodium ion, a potassium ion, or a magnesium ion. Such a compound is particularly excellent in the effect of improving the crystallization rate.

Specific examples of compound (XVa) include, for example, lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, zinc dehydroabietic acid, dehydroabietic acid. Metal salts of dehydroabietic acid such as aluminum abietic acid and the like can be mentioned, and sodium dehydroabietic acid, potassium dehydroabietic acid and magnesium dehydroabietic acid are preferably used.

Specific examples of the compound (XVb) include, for example, lithium dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, beryllium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, zinc dihydroabietic acid, and dihydroabietic acid. Examples thereof include metal salts of dihydroabietic acid such as aluminum abietic acid, and sodium dihydroabietic acid, potassium dihydroabietic acid, and magnesium dihydroabietic acid are preferably used.

In the present invention, at least two kinds of rosin acid partial metal salts may be used as nucleating agents. This at least 2
The species of rosin acid partial metal salts may include at least two metal rosin acid salts having the same rosin acid and different metals, including at least two metal rosin acid salts having different rosin acids and the same metal. It may contain at least two kinds of rosin acid metal salts having different rosin acids and different metals. It is preferable that at least two kinds of rosin acid partial metal salts contain rosin acid metal salts in a total amount of 5 to 100% by weight, preferably 10 to 100% by weight.

The amount ratio of the rosin metal salt in the at least two kinds of rosin acid partial metal salts is arbitrary, but is not limited to one kind relative to the total amount of the rosin metal salts in at least two kinds of rosin acid metal salts. Is more than 0 mol%, preferably 5 to 95 mol%, and at least one other metal rosin acid salt is less than 100 mol%, preferably 95 to 5 mol%. It is desirable.

As a combination of at least two kinds of rosin acid partial metal salts, a combination of a rosin acid partial potassium salt and a rosin acid partial sodium salt or a rosin acid partial magnesium salt is preferable. Further, potassium rosinate is 20 mol% or more, preferably 40 to 95 mol%, based on the total amount of metal rosinate in two kinds of partial metal salts of rosin.
Mol%, more preferably 45 to 80 mol%, and sodium rosinate or magnesium rosinate is combined in a proportion of less than 80 mol%, preferably 60 to 5 mol%, more preferably 55 to 20 mol%. It is desirable. Such a partial metal salt of rosin acid containing at least two kinds of metals is more excellent in dispersibility in a thermoplastic resin than a partial metal salt of rosin acid containing only one kind of metal.

<Metal Deactivator> As the metal deactivator used in the present invention, compounds conventionally used for improving the deterioration of resin by various metals can be used without any particular limitation.

The metal deactivator used in the present invention includes:
For example, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine (trade name IRGANOX MD1 manufactured by Ciba Geigy)
024), distearyl hydrazine, dilauroyl hydrazine, dicaproyl hydrazine, dioctanoyl hydrazine, N, N'-bis (2-ethylhexanoyl) hydrazine, salcytoyl-benzoyl hydrazine, salicylidenesalicyloyl hydrazine (Ciba Geigy) Made,
Hydrazine compounds such as trade name Chel-180);
Bis (α-phenoxypropionyl) hydrazide isophthalate, oxalo-bis-12-hydroxybenzylidene hydrazide (manufactured by Eastman Kodak, trade name Eastman Inhibitor OABH), bis-salicyloyl (β, β′-thiodipropionate) hydrazide And hydrazide compounds such as bis-acetoadipate hydrazide (Ciba Geigy, trade name GI09-367), decamethylene dicarboxylic acid disalicyloyl hydrazide (Adeka Argus Co., trade name Adekastab CDA-6); 3- ( N-salicyloyl) amino-1,2,4-triazole (Adeka Argus Co., Ltd., trade name Adekastab CDA-1), benzotriazole, 3-amino-
Examples include nitrogen-containing aromatic compounds such as 1,2,4-triazole, 1,3-diphenyltriazine, and 5-phenyltetrazole.

In addition, N-salicyloyl-N'-aldehydeazine, N, N-dibenzal (oxalhydrazide), N, N-bis (3,5-di-t-butyl-hydroxyhydrocinnamate) , 2,2'-oxamido-bis-ethyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate and the like. The metal deactivator may be used alone,
Two or more can be used in combination.

Among the above metal deactivators, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine (trade name IRGANOX MD1024, manufactured by Ciba Geigy). Bis (α-phenoxypropionyl) hydrazide isophthalate,
3- (N-salicyloyl) amino-1,2,4-triazole (Adeka Argus Co., trade name Adekastab C)
DA-1), 2,2'-oxamide-bis-ethyl-3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Uniroyal Corporation, trade name: Nau
guard XL-1) is preferred.

In the present invention, by blending the above metal deactivator, copper, cobalt, iron, vanadium, nickel, titanium, calcium, silver, zinc, aluminum, magnesium, lead, chromium, manganese, A polyolefin, particularly a propylene-based polymer composition, which can prevent deterioration due to metals such as cadmium, tin, zirconium, and hafnium, and has excellent metal deterioration resistance, particularly at high temperatures, can be obtained. For this reason, the composition of the present invention does not change its properties even in a state of being in direct contact with a metal, and is excellent in long-term stability.

In the present invention, when one or two or more hydroxides such as magnesium hydroxide, aluminum hydroxide or calcium hydroxide are used in combination with the above-mentioned metal deactivator, the synergistic effect of the two can be obtained. The effect can significantly reduce the deterioration of the resin due to the metal. The amount of the hydroxide is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin.

<Lubricant> As the lubricant used in the present invention, those conventionally used as a resin lubricant can be used without any particular limitation. The following compounds are used as specific lubricants. Synthetic hydrocarbons such as Tropsch wax and polyethylene wax; Synthetic modified waxes such as montan wax derivatives, paraffin wax derivatives and microcrystalline wax derivatives; Synthetic hydrogenation such as hydrogenated castor oil, hydrogenated rapeseed oil derivatives, hydrogenated rapeseed oil and hydrogenated soybean oil Wax; Ca stearate, Ba stearate, Z stearate
n, synthetic metal soaps such as stearic acid Li; synthetic higher fatty acids such as stearic acid and 12-hydroxystearic acid; synthetic fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, ethylenebisstearic acid amide, EBS; Synthetic fatty acid esters such as butyl stearate and long-chain fatty acid esters; and synthetic higher alcohols such as cetanol and stearyl alcohol.

Commercially available lubricants can be used. For example, Armoslip CP (manufactured by Lion Corporation,
Trademark), Neutron 2 (trademark, manufactured by Nippon Seika Co., Ltd.),
Alflow P-10 (trademark, manufactured by NOF Corporation), Armowax EBS (trademark, manufactured by Lion Armor Co., Ltd.)
And the like. These lubricants can be used alone or in combination. The amount of the lubricant is preferably 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.05 to 1 part by weight based on 100 parts by weight of the thermoplastic resin.

When the blending amount of the lubricant is within the above range with respect to 100 parts by weight of the thermoplastic resin, the fluidity when the propylene-based polymer composition of the present invention is melted by heating and molded is improved. In addition, the adhesiveness to the molding machine and the mold is suppressed, the mold release of the molded body is improved, and when formed into a film, the slip properties such as opening are improved,
Moreover, the properties of the thermoplastic resin, for example, tensile strength and the like do not decrease. Furthermore, since metal salts of higher fatty acids such as Ca stearate have an effect not only as a lubricant but also as a rust inhibitor, a propylene-based polymer composition containing such a metal salt of higher fatty acids has excellent releasability. It is effective in preventing rust in molding machines.

<Anti-blocking agent> As the anti-blocking agent, for example, synthetic or natural silica, silicon dioxide, talc, zeolite and the like are used. The average particle size of these antiblocking agents is preferably 5 μm.
Or less, more preferably 4 μm or less. When the average particle size is in such a range, a film having good transparency and zero scratch property can be obtained.

The water content of the antiblocking agent is preferably 15% by weight or less, more preferably 5% by weight or less. It is preferable to use an antiblocking agent having a water content in the above range, since foaming does not occur during film formation. Anti-blocking agents
Preferably, 0.0 parts by weight per 100 parts by weight of the thermoplastic resin.
It is used in an amount of 1 to 0.5 part by weight, more preferably 0.05 to 0.2 part by weight.

<Slip agent> Examples of the slip agent include one or two of a linear monocarboxylic acid monoamide compound and a linear monocarboxylic acid bisamide compound.
It can be used in combination of more than one species.

Examples of the linear monocarboxylic acid monoamide compound include oleic amide, stearic amide, erucic amide, palmitic amide, behenic amide, lauric amide and the like. Examples of the linear monocarboxylic acid bisamide compound include ethylene bisoleic acid amide, ethylene bis stearic acid amide, and methylene bis stearic acid amide.

From the viewpoint of the film slip property at the time of molding and the film slip property after the molding, it is preferable to use a linear monocarboxylic acid monoamide compound alone.
In the case of the polypropylene film laminate according to the present invention described below, it is preferable to use a linear monocarboxylic acid monoamide compound and a linear monocarboxylic acid bisamide compound in combination from the viewpoint of slip properties after lamination. .

The above-mentioned slip agent is preferably used in an amount of 0.01 to 1.0 based on 100 parts by weight of the thermoplastic resin.
0 parts by weight, more preferably 0.03 to 0.5 parts by weight, particularly preferably 0.05 to 0.2 parts by weight. When using a linear monocarboxylic acid monoamide compound and a linear monocarboxylic acid bisamide compound in combination,
The weight ratio of linear monocarboxylic acid monoamide compound / linear monocarboxylic acid bisamide compound is preferably 20/80 to 80/20, more preferably 30/7.
It is desirable to be in the range of 0 to 70/30.

<Heat Insulating Agent> In the present invention, in order to improve the heat insulating property, an inorganic filler such as silica, a magnesium compound and hydrotalcite, and a water absorbing resin such as an ethylene-vinyl alcohol copolymer can be added.
Among these, it is desirable to use hydrotalcite compounds.

The hydrotalcite compounds used in the present invention are exemplified by the following structures. Hydrotalcite group; general formula Mg ₆ R ₂ (OH) ₁₆ CO ₃ / 4H ₂ O (R
= Al, Cr, Fe) Hydrocarbonate minerals (natural minerals slightly generated in the Raul region of the USSR, the Sunarm region of Norway, etc.) Synthetic hydrotalcites described below M 2 ⁺ _{1 -x} Al _x (OH) ₂ (A ⁿ⁻ ) _{x / n} · mH ₂ O
(. Provided that 0 <x <0.5,0 ≦ m ≦ 2) M 2+: Mg, Ca, selected from Zn divalent metal ions A ^n-: n-valent anion, eg, Cl ^- , Br ^-, I
^{_{-, NO 3 -, ClO 4}} -, SO 4 2-, CO 3 2-, SiO 3
^{_{2-, HPO 4 2-, HBO 3}} 2-, PO 4 3-, Fe (C
^{_{N) 6 3-, Fe (CN}} ) 4 4-, CH 3 COO -, C 6 H
₄ (OH) COO ⁻ , (OOC-COO) ²⁻ , and the like.

The average particle size of these hydrotalcite compounds is not particularly limited as long as it does not adversely affect the appearance of the film, the elongation or the formability, and is not particularly limited. Is 5μ or less, more preferably 3μ or less. In addition, in order to improve the dispersibility of the hydrotalcite compound, it is preferable to use the hydrotalcite compound after treating it with a surface treating agent. Examples of surface treatment agents include paraffin, fatty acids, higher alcohols,
Examples include a polyhydric alcohol, a thionate-based coupling agent, and a silane-based coupling agent.

The amount of the hydrotalcite compound to be used is appropriately selected at a thermoplastic resin / hydrotalcite compound = 98 to 60/2 to 40 weight ratio. More preferably, the ratio is from 98 to 75/2 to 25 by weight.

<Fogproofing agent> The fogproofing agent used in the present invention includes:
Surfactants in which part or all of H is bonded to C of the hydrophobic group of a normal surfactant are substituted with F, and especially a fluorine-based surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group is used. preferable. Representative examples of the fluorine-based surfactant that can be used in the present invention are as follows.

(A) Anionic fluorinated surfactant (1) -COOM R_f COOM R_f SO_Two N (R ')_Two CH_Two COOM (2) -OSO_Three M system R_f BNR 'YOSO_Three M (3) -SO_Three M system R_f SO_Three M R_f CH_Two O (CH_Two )_m SO_Three M(4) -OPO (OM)_Two System R_f BNR 'YOP (= O) (NM)_Two In each of the above formulas, R_f And R '_fIs one of the hydrogen atoms of the alkyl group
Fluoroalkyl substituted partially or entirely with a fluorine atom
B represents -CO-, -CO_Two -, -SO _Two -
R ′ represents a hydrogen atom or a lower alkyl group;
Atom, -NH_Four, Alkali metals and alkaline earth metals
You.

The above fluoroalkyl group is preferably a polyfluoroalkyl group having the following structure. CF _3- (CF ₂ ) _l -l is an integer of 2 to 19 HCF _2- (CF ₂ ) _n -n is an integer of 2 to 19

In the present invention, R _f and R ′ _f include, in addition to the fluoroalkyl group, CF ₂ ＝ CF ₂ ,
A branched polyfluoroalkyl group synthesized by the oligomerization of F ₃ —CF ＝ CF ₂ , C ₃ F ₇ O
— (C ₃ F ₆ O) _k CO— [k is an integer of 0 to 5].

(B) Cationic fluorinated surfactant

Embedded image Wherein R _f , B, R ′ _f and Y have the same meaning as described above,
R ″ represents a hydrogen atom or a lower alkyl group, HX represents an acid, X represents a halogen or an acid radical.

(C) Amphoteric fluorinated surfactant (1) —N ⁺ (R ′) ₂ —COO ⁻ system R _f BNHYN ⁺ (R ′) ₂ (CH ₂ ) _m COO ^{— wherein} R _f and B , _R'f and Y have the same meaning as described above.

(D) Nonionic fluorine-based surfactant (1) -OH-based R_f OH (2) -O- systemWhere R_f , B and R ′ have the same meaning as described above, and Y is
-CH_Two -, -C_Two H _Four OCH_Two Represents-, and Z is a hydrogen atom
And —C (＝ O) R and —C (＝ O) NHR. here
And R is a hydrogen atom or a lower alkyl having 1 to 5 carbon atoms.
(Hereinafter the same)

Preferred examples of the above-mentioned and other types of fluorine-based surfactants are as follows. (i) C _n F _{2n + 1} COOM where M = hydrogen atom, alkali metal, —NH ₄ , n = 5
To 12, preferably 6 to 10, for example, C ₉ F ₁₉ COONa C ₅ F ₁₇ COOLi (ii) C _n F _{2n + 1} CONH (C ₂ H ₄ O) _m H where n = 5 to 12, preferably Is 6 to 10, m
= 1 to 30, preferably 2 to 20, for example C ₉ F ₁₉ CONH (C ₂ H ₄ O) ₃ H

(Iii)

Embedded image Wherein R = hydrogen atom, lower alkyl group, n = 6 to 1
2, preferably 9, m = 2 to 30, preferably 3 to 20, for example,

Embedded image

(Iv) C _n F _{2n + 1} CONHC ₃ H ₆ N ⁺
_{(CH 3) 2 C 2 H} 4 COO - where, n = 5 to 12, preferably 6 to 10, for _{example, C 9 F 17 CONHC 3 H} 6 N + (CH 3) 2 C 2 H 4 C
OO ^-

(V) C _n F _{2n + 1} CONHC ₃ H ₆ N ⁺
(CH _{3) 2} · X ^- wherein, X = halogen acid radical, n = 5 to 12, preferably 6 to 10, for _{example, C 8 F 17 CONHC 3 H} 6 N + (CH 3) 2 · I -

(Vi) C _n F _{2n + 1} (CH ₂ ) _m COOM where M = hydrogen atom, alkali metal, —NH ₄ , n = 3
To 12, preferably 5 to 10, m = 1 to 1
6, preferably 2 to 10, for _{example, C 7 F 15 (CH 2} ) 5 COONa C 8 F 17 (CH 2) 4 COOK

(Vii) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ ) C ₂
H ₄ OPO (OH) _{2 wherein} n = 5 to 12, preferably 6 to 10, for example, C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OPO (OH)
_Two

(Viii) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ )
CH ₂ COOM where M = hydrogen atom, alkali metal, —NH ₄ , n = 5
To 12, preferably 6 to 10, for example, C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ COOK

(Ix) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ ) C ₂
H ₄ OSO ₃ H wherein n = 5 to 12, preferably 6 to 10, for example, C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OSO ₃ H

(X) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ ) (C ₂
H ₄ O) _m H wherein n = 5 to 12, preferably 6 to 10, m
= 1 to 30, preferably 2 to 20, for _{example, C 8 F 17 SO 2 N} (C 2 H 5) (C 2 H 4 O) 14 H

[0133] _{(xi) C n F 2n +} 1 CON (C 2 H 5) (C 2
H ₄ O) _m H wherein n = 5 to 12, preferably 6 to 10, m
= 1 to 30, preferably 2 to 20, for _{example, C 8 F 17 CON (C} 2 H 5) (C 2 H 4 O) 14 H

[0134] Wherein n = 5 to 12, preferably 6 to 10, m
= 1 to 30, preferably 2 to 20, Y is -CH
_{2 -, - C 2 H 4} OCH 2 - represents, Z is a hydrogen atom, -
C (= O) R, -C (= O) NHR, for example,

[0135] Wherein n = 5 to 12, preferably 6 to 10, m
= 1 to 30, preferably 2 to 20, Y is -CH
_{2 -, - C 2 H 4} OCH 2 - represents, Z is a hydrogen atom, -
C (= O) R, -C (= O) NHR, for example,

(Xiv) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ ) (C ₂ H ₄ O) _m C ₂ H ₄ N
(C ₂ H ₅ ) SO ₂ C _n F _{2n + 1 wherein} n = 5 to 12, preferably 6 to 10, m
= 1 to 30, preferably 2 to 20, for _{example, C 8 F 17 SO 2 N} (C 2 H 5) (C 2 H 4 O) 14 C 2 H 4 N (C 2 H 5) SO 2 C 8 F ₁₇

[0137] Wherein n = 5 to 12, preferably 6 to 10, m
= 1 to 30, preferably 2 to 20, l = 1 to 30, preferably 2 to 20, for example, The above-mentioned fluorine-based surfactants can be used alone or in combination of two or more.

The amount of the fluorosurfactant to be added is not critical and can be varied widely depending on the type of the fluorosurfactant to be blended and the type of the resin. It can be at least 0.01 part by weight per 100 parts by weight of the thermoplastic resin. The upper limit of the blending amount is not strictly limited, but if the blending amount is too large, bleed out or cloudiness may be caused. Therefore, 2.0 parts by weight or less is usually sufficient.

[0139]

The antifogging molded article according to the present invention exhibits antistatic and antifogging properties immediately after molding since the antifogging agent is dispersed in the thermoplastic resin at a specific particle size, and Has stable performance over a long period. The form of the antifogging molded article of the present invention is not particularly limited as long as the surface satisfies the above requirements. For example, any form such as a film, a sheet, a bottle, a panel, and a plate may be used. Further, the antifogging molded article of the present invention is not limited to a molding method, and is obtained by a molding method known per se such as an injection molding method, an extrusion molding method, and a stretch molding method. When the molded body is a film, a short screw extruder, a kneading extruder, a ram extruder, a gear extruder, and the like are used.
It can be manufactured by extruding a molten thermoplastic resin composition from a T-die. As the molding conditions, conventionally known conditions can also be adopted. The film may be stretched, and the stretched film is formed by using a sheet or film made of the thermoplastic resin composition as described above, using a conventionally known stretching apparatus, and using a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), It can be manufactured by a biaxial stretching method, a uniaxial stretching method, or the like. Further, the film may be manufactured by a blown film molding method. Further, the film according to the present invention exhibits antistatic performance and antifogging performance immediately after molding, and is excellent in antifogging durability and antistatic durability as compared with conventional films.

[0140]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the examples are for describing preferred embodiments of the present invention, and the present invention is not limited to these examples. It is not something to be done. The average particle diameter, Lw / Lh, and average distance between the centers of gravity in Examples and Comparative Examples were measured by taking a transmission electron microscope photograph of a cross section of the film and using an image processing apparatus (IP-1000) manufactured by Asahi Kasei Corporation. Was calculated. The values of the solubility parameter (Xb) of the antifogging agent in Examples and Comparative Examples are determined by the molecular volume (ΔVi) of each functional group constituting the molecule and the evaporation energy (Δe).
From i), it was determined by the following equation. Xb = (ΣΔei / ΣΔVi) ^1/2

The antifogging properties of the films in Examples and Comparative Examples were evaluated as follows. <Initial anti-fogging property> 70 cc of water was placed in a 100 cc beaker, and the upper surface thereof was covered with the inner layer of the sample film facing down.
In a constant temperature room. The degree of haze on the inner surface of the sample film was observed after 24 hours. Evaluation criteria: ：: No water droplets were observed in the flowing state. Δ: Large water droplets partially adhered to the film. ×: Fine water droplets adhered to almost the entire surface of the film.

<Persistence of anti-fogging> The sample film was immersed in warm water at 60 ° C., taken out from the warm water after 40 days and dried, and the anti-fogging property after 24 hours was observed and evaluated by the above method.

<Measurement of Dispersion State> The measurement of the average particle diameter, Lw / Lh, and average center of gravity of the antifogging agent-dispersed particles on the surface of the molded product was performed by taking a transmission electron micrograph of the cross section of the film.
Image processing equipment (IP-1000) manufactured by Asahi Chemical Industry Co., Ltd.
It measured using.

<Production Example 1> Preparation of ethylene / 1-hexene copolymer [Preparation of catalyst for olefin polymerization] 5.0 kg of silica dried at 250 ° C for 10 hours was suspended in 80 l of toluene, and then suspended. Cooled to 0 ° C. Thereafter, 28.7 l of a toluene solution of methylaluminoxane (Al; 1.33 mol / l) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the reaction was carried out at 0 ° C. for 60 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 20 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended with 80 liters of toluene. 7.4 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / L) and bis (1,3-dimethylcyclopentadienyl) were introduced into the system. ) Zirconium dichloride in toluene solution (Zr; 2)
(8.1 mmol / l) 1.0 liter was added dropwise at 80 ° C. over 30 minutes, and further reacted at 80 ° C. for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per gram.

[Preparation of prepolymerized catalyst] In 85 liters of hexane containing 1.7 mol of triisobutylaluminum, 0.85 kg of the solid catalyst obtained above and 1
Hexene (255 g) and ethylene prepolymerization at 35 ° C. for 12 hours to give 10 g / g solid catalyst.
g of polyethylene was prepolymerized to obtain a prepolymerized catalyst. The intrinsic viscosity [η] of this ethylene polymer is 1.74 d.
1 / g.

[Polymerization] Two continuous fluidized-bed gas-phase polymerization apparatuses connected in series were used in the presence of the above pre-polymerization catalyst.
The copolymerization of ethylene and 1-hexene is performed to obtain ethylene.
A 1-hexene copolymer (PE-1) was obtained. The ethylene / 1-hexene copolymer (PE
-1) has a 1-hexene content of 13.5% by weight,
The density is 0.908 g / cm ³ and the MFR (ASTM
D1238-65T, 190 ° C, load 2.16kg)
Was 1.95 g / 10 min, and the molecular weight distribution (Mw / Mn) measured by GPC was 3.0. In addition, this copolymer had an n-decane soluble component fraction [W] at room temperature of 0.54% by weight. Further, the solubility parameter (Xa) of this copolymer determined by calculation was 8.48.

<Production Example 2> [Synthesis of antifogging agent] 578 g of montanic acid wax (trade name “Hoechst wax S”, manufactured by Hoechst) and polyoxyethylene lauryl in a 2-liter separable flask made of glass under a nitrogen atmosphere. 422 g of ether (containing 5 mol of oxyethylene unit) and 2.5 g of methanesulfonic acid were charged, and the temperature was raised to 190 ° C. with stirring to melt the reaction mixture. Next, 5 mmH
g, and reacted for 4 hours while continuing stirring. After the completion of the reaction, the reaction mixture in a molten state was taken out and allowed to cool to room temperature to obtain an antifogging agent (hereinafter, referred to as “W-1”). The weight average molecular weight of the obtained W-1 was measured by gel permeation chromatography and found to be 670.

<Production Examples 3 to 5> Production Example 2 was conducted except that the polyolefin wax containing a higher fatty acid or carboxylic acid and the polyoxyalkylene-containing compound shown in Table 1 were used.
A triblock oligomer was synthesized in the same manner as described above. Table 1 shows the results.

[0150]

[Table 1]

<Examples 1 and 2> After the compositions having the constitutions shown in Table 2 were mixed under the following conditions, a film having a thickness of 100 μm was blown-molded under the following conditions. Table 2 shows the evaluation results of the obtained films. [Mixing conditions] Extruder: 30 mmφ twin screw extruder manufactured by Placo, mixing temperature: 190 ° C [Inflation molding conditions] Molding machine: Inflation molding machine manufactured by Alpine, die diameter: 400 mm, molding temperature: 200 ° C, folding width: 1500
mm

<Comparative Examples 1 to 3> Films were formed in the same manner as in Example 1 except that the compositions having the compositions shown in Table 2 were used. Table 2 shows the evaluation results of the obtained films.

[0153]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 3/18 C09K 3/18 101 101

Claims (8)

[Claims] 1. The thermoplastic resin (A) has a ratio (O / C) of the number of oxygen atoms to the number of carbon atoms on the surface of the molded body of at least 10/100, and has a thickness of at least 5 μm from the surface of the molded body. In the range, the antifogging agent (B) has an average particle diameter of 0.05 to 0.5 μm; an average value (Lw) of the particle diameter in the long axis direction and an average value (Lh) of the particle diameter in the short axis direction of the dispersed particles. ), And Lw / Lh is 3.0 or less; and the average value of the distance between the centers of gravity of the dispersed particles is 1.5 μm or less. body. 2. The antifogging agent (B) has the following (I)
The antifogging molded article according to claim 1, comprising at least one of the polar groups represented by (V) to (V). -(R ¹ -O) _n -R ² (I) (wherein R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, 1 to 22 carbon atoms) Represents a linear or branched alkyl group.
Represents an integer of 1 to 30. _{) -OH (II) -SO 3 X} (III) ( wherein, X represents a hydrogen atom, Na, K, representing a _{^{Li) -N + R 3 X -}} (IV) ( wherein three of R respectively also same thing may be different, having 1 to hydrogen atom or a C represent 3 alkyl group, X is Cl, represents Br or _{^{I) -N + R 2 COO -}} (V) ( wherein, 2 pieces R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) 3. The antifogging agent (B) has a weight average molecular weight of 100 as measured by gel permeation chromatography.
To 8,000, and the thermoplastic resin (A)
Absolute value (dX = |) of the difference between the value of the solubility parameter (Xa) and the value of the solubility parameter (Xb) of the antifogging agent (B).
3. The antifogging molded article according to claim 1, wherein Xa-Xb |) is 0 to 1 (cal / ml) ^1/2 . 4. The antifogging agent (B) has a weight average molecular weight of 10 as measured by gel permeation chromatography.
The anti-fogging molded article according to claim 3, wherein the molded article has a range of 0 to 5,000. 5. The thermoplastic resin (A) is a polyolefin, and the value of the solubility parameter of the antifogging agent (B) is in the range of 7 to 9 (cal / ml) ^1/2.
Or the anti-fogging molded article according to 2. 6. The anti-fogging agent (B) comprises a carboxylic acid-containing polyolefin wax (C) or a higher fatty acid having 16 or more carbon atoms and its derivative (D), and a polyoxyalkylene-containing polyoxyalkylene represented by the following formula VI: The antifogging molded article according to claim 1, which is a reaction product with the compound (E). X- (R ¹ -O) _n -R ² (VI) (where X represents OH or NH ₂ , and R ¹ has ¹ carbon atom)
Represents a linear or branched alkyl group of
R ² represents a linear or branched alkyl group having 1 to 22 carbon atoms. n represents an integer of 1 to 30) 7. The antifogging molded article according to claim 1, wherein the molded article is a film. 8. The antifogging molded article according to claim 7, wherein the film is an agricultural film.