JP2000053841A - Matting agent for flexible film and matted flexible film containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a matting agent for a flexible film which imparts excellent matting properties to a thermoplastic flexible film without detriment to flexibility, tenacity and touch as well as without causing whitening phenomenon in bending or stretching of the film. SOLUTION: This matting agent comprises a particle having a multiphase structure obtained by a first step reaction wherein a rubbery polymer having a glass transition temperature of 20 deg.C or lower is formed by a radical polymerization of a polymerizable monomer (I) capable of forming a rubbery polymer and a subsequent second step reaction wherein a polymerizable monomer (II) capable of forming a glassy polymer having a glass transition temperature of at least 50 deg.C is added thereto to effect a radical polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention impairs the flexibility, toughness and texture of a film by blending it into a thermoplastic soft film or sheet (both of which are hereinafter referred to as a film). The present invention relates to a matting agent for a soft film which imparts excellent matting properties to a film without squeezing, and a matte soft film containing the same.

[0002]

2. Description of the Related Art Thermoplastic soft films are used for wallpaper, interior materials for decorative panels, housing devices for home appliances,
It is widely used as an overlay film or a protective film for the interior panel of automobiles, but its surface is required to have a deep matte with low gloss. Until now, as a matting agent for films, particles of inorganic compounds such as silica and glassy polymer particles such as polymethyl methacrylate and polystyrene have been used. Is characterized by the fact that a transparent matting property can be obtained. However, when the above glassy polymer particles are kneaded as a matting agent into a soft film of polyolefin, acrylic, polyester, nylon, polyurethane, etc., not only the flexibility, toughness and texture of the soft film are impaired, but also the bending and There are drawbacks such as whitening during stretching and loss of transparency. It is considered that these causes are due to the difficulty of the glassy polymer particles following the stress applied during stretching or bending of the soft film.

In order to solve this problem, rubber-like polymer particles, for example, particles obtained by copolymerizing a lower alkyl acrylate and a polyfunctional vinyl monomer (JP-A-3-3720)
1) particles obtained by copolymerizing a lower alkyl acrylate and a polyfunctional urethane (meth) acrylate (Japanese Patent Laid-Open No. 4-65)
405) and the like have been proposed to be incorporated into a flexible film. Increasing the monomer content that provides these rubber-like polymers such as lower alkyl acrylates can provide softer and more elastic polymer particles, which can solve the above problems to some extent. However, as a major problem when using rubber-like polymer particles, when the content of a lower alkyl acrylate having a low glass transition point is increased, aggregation and fusion of the particles at the synthesis stage when manufacturing by suspension polymerization, Coupling may occur. Furthermore, since the polymer particles are aggregated and fused by heating during dehydration or drying after completion of the synthesis, it may not be possible to take out the product while maintaining the shape as particles. Also, even if these polymer particles are obtained, handling problems such as blocking, and when kneaded and blended into a flexible film, because the polymer particles do not disperse to the primary particles in the film, sufficient matte In addition to the lack of properties, problems such as a very poor appearance of the film occur.

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to prevent the fineness of the flexible film itself from being lost while retaining the elasticity of the flexible film in order not to impair the flexibility, toughness and texture of the soft film. An object of the present invention is to provide a matting agent for a flexible film having improved properties. Furthermore, by kneading the matting agent for a soft film, it is another object of the present invention to provide a matt-like soft film having a transparent feeling and excellent matting properties.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have formed a rubber-like polymer by radical polymerization (first-stage reaction), and subsequently a monomer which forms a glass-like polymer. It has been found that polymer particles having a multi-phase structure that can solve the above-mentioned problems can be obtained by the operation of performing radical polymerization (second-stage reaction) by adding a polymer. The multi-phase structure in the present invention refers to a structure in which a polymer formed in the first-stage reaction and a polymer formed in the second-stage reaction exist as different phases in one particle, respectively. In addition to the above-mentioned multilayer structure and salami structure, a structure in which the surface of the particles of the first reaction is partially covered with the polymer of the second reaction is also included. Since the surface of the polymer particles is covered with a hard polymer, there is no fusion between the particles due to dehydration and drying during production. Also, when used as a matting agent for soft films, it is easy to disperse at the time of kneading, and the processed film maintains flexibility, toughness, texture, without whitening or reduction in strength during bending or stretching, It was found that a matte with a transparent feeling was obtained. That is, the present invention provides (1) a first-stage reaction of forming a rubber-like polymer having a glass transition temperature of 20 ° C. or less by radical polymerization of a polymerizable monomer (I) which forms a rubber-like polymer, and subsequently, a glass-transition temperature of 50 ° C. A matting agent for a flexible film containing multi-phase structured particles produced by a second-stage reaction of adding a polymerizable monomer (II) which forms a glassy polymer at a temperature of not less than ℃, (2) a first-stage The matting agent for a flexible film according to the above (1), wherein the radical polymerization in the reaction is suspension polymerization,
(3) The weight average particle diameter of the multiphase structure particles is 2 to 100 μm
The matting agent for a flexible film according to the above (1),
(4) Polymerizable monomer (I) forming rubbery polymer
Is an alkyl (meth) acrylate (a) 50 to 99.
A monomer mixture comprising 9% by weight, 0.1 to 20% by weight of a polyfunctional monomer having two or more vinyl groups in a molecule (b) and 0 to 49.9% by weight of another copolymerizable monomer (c) The matting agent for a flexible film according to the above (1),

(5) The polymerizable monomer (II) forming the glassy polymer is 50 to 100% by weight of at least one monomer selected from an alkyl (meth) acrylate (d) and an aromatic vinyl monomer (e). A monomer or monomer mixture consisting of 0 to 10% by weight of a polyfunctional monomer (f) having two or more vinyl groups in a molecule and 0 to 50% by weight of another copolymerizable monomer (g); The matting agent for a flexible film according to (1), wherein (6) the polymerizable monomer (II) forming the glassy polymer is at least one selected from alkyl (meth) acrylate (d) and aromatic vinyl monomer (e) 50 to 99.5% by weight of a polyfunctional monomer (f) having two or more vinyl groups in the molecule.
% By weight and urethane (meth) acrylate 0.5 to 3
0.5 g of other copolymerizable monomer containing 0% by weight
A matting agent for a soft film according to the above (5), wherein the soft film is a soft urethane film; and (7) the weight ratio of the rubbery polymer to the glassy polymer is 95/5 to 5% by weight. 30/70, the matting agent for a flexible film according to the above (1), and (8) a polymerizable monomer (I
The matting agent for a flexible film according to the above (1), wherein the emulsion containing the surfactant (I) and the surfactant is added to the first-stage reaction solution to absorb or adhere to the first-stage particles to perform radical polymerization. A matte soft film containing the matting agent for a soft film according to any one of the above (1) to (8),
And (10) The matte soft film as described in (9) above, wherein the soft film matting agent is contained in an amount of 3 to 200 parts by weight with respect to 100 parts by weight of the soft film.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The first reaction in the present invention is a polymerizable monomer (I) which forms a rubbery polymer by polymerization.
Is a reaction for forming a rubbery polymer having a glass transition temperature of 20 ° C. or less by radical polymerization, particularly suspension polymerization. Preferred as the polymerizable monomer for forming the rubbery polymer is an alkyl (meth) acrylate (a) 5
0 to 99.9% by weight, 0.1 to 20% by weight of a polyfunctional monomer having two or more vinyl groups in the molecule (b) and 0 to 49.9% by weight of another copolymerizable monomer (c) Is a monomer mixture consisting of The above alkyl (meth)
Examples of the acrylate (a) include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and lauroyl (meth). An alkyl (meth) acrylate having 2 to 20 carbon atoms in the alkyl group such as acrylate and stearyl (meth) acrylate can be given. Among them, those having an alkyl group having 2 to 10 carbon atoms such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isononyl (meth) acrylate are preferable, and butyl acrylate, 2-ethylhexyl acrylate and isononyl acrylate are particularly preferable. preferable. This alkyl (meth) acrylate is usually 50 to 99.9% by weight, preferably 6 to 9% by weight, of the polymerizable monomer (I) forming the rubbery polymer.
It is used in the range of 0 to 99.9% by weight.

When the glass transition temperature of the rubbery polymer is higher than 20 ° C., sufficient flexibility of the film,
Toughness and texture may not be obtained. Therefore,
The glass transition temperature of the rubbery polymer is preferably from -60 to 20C, more preferably from -60 to 10C. In this first-stage reaction, by using a polyfunctional monomer (b) having two or more vinyl groups in the molecule, it is possible to control the elastic modulus of the rubber-like polymer or impart heat resistance, solvent resistance, and the like. Becomes possible. Examples of the polyfunctional monomer (b) having two or more vinyl groups in the molecule include aromatic divinyl monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, and hexanediol di ( (Meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane di (meth)
Examples of monomers having a different reactive vinyl group, such as alkane polyol polyacrylate or alkane polyol polymethacrylate such as acrylate and trimethylolpropane tri (meth) acrylate, include, for example, allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate And urethane di (meth) acrylate, epoxy di (meth) acrylate, etc., among which ethylene glycol dimethacrylate, butylene glycol diacrylate and allyl methacrylate are particularly preferably used.

The polyfunctional monomer (b) having two or more vinyl groups in the molecule is usually contained in an amount of 0.1 to 20% by weight in the polymerizable monomer (I) forming the rubbery polymer.
Preferably, it is used in the range of 0.1 to 10% by weight. Further, as the copolymerizable monomer (c) copolymerizable with (a) and (b) in the first-stage reaction, for example, aromatic vinyl such as styrene, vinyltoluene, α-methylstyrene, aromatic vinylidene, acrylonitrile, Vinyl cyanide such as methacrylonitrile, vinylidene cyanide,
Examples include urethane acrylate and urethane methacrylate. Also epoxy group, carboxyl group,
A monomer having a functional group such as a hydroxyl group or an amino group may be copolymerized. For example, as a monomer having an epoxy group, glycidyl methacrylate and the like can be mentioned, and as a monomer having a carboxyl group, methacrylic acid,
Acrylic acid, maleic acid, itaconic acid and the like can be mentioned.
Examples of the monomer having a hydroxyl group include 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate. Examples of the monomer having an amino group include diethylaminoethyl methacrylate and diethylaminoethyl acrylate.

[0010] These copolymerizable monomers (c) are usually contained in the polymerizable monomer (I) which forms a rubber-like polymer.
To 49.9% by weight, preferably 0 to 39.9% by weight. This first-stage reaction comprises the above-mentioned polymerizable monomer (I) forming a rubbery polymer, a dispersion stabilizer,
An oil-soluble radical polymerization initiator and ion-exchanged water are charged into a polymerization vessel, and radical polymerization, preferably suspension polymerization, is performed with stirring. It is preferable that the oil-soluble radical polymerization initiator is dissolved in the polymerizable monomer in advance. Examples of the dispersion stabilizer include gelatin, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polyacrylamide, polyacrylic acid, polyacrylate, sodium alginate ,
Water-soluble polymers such as partially saponified polyvinyl alcohol,
Examples thereof include inorganic substances such as tricalcium phosphate, titanium oxide, calcium carbonate, and silicon dioxide. Of these dispersion stabilizers, polyvinyl alcohol partially saponified, hydroxypropylcellulose, and tricalcium phosphate are particularly preferably used. One or more of these dispersion stabilizers can be used.

The amount of the dispersion stabilizer used is, for example, 0.1 to 100 parts by weight of the polymerizable monomer (I) in the first stage reaction.
It is 30 parts by weight, preferably about 0.5 to 10 parts by weight. Examples of the oil-soluble radical initiator include organic peroxides such as benzoyl peroxide, o-methoxybenzoyl peroxide, o-chlorobenzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and 2,2′-azobis. Examples include azo compounds such as isobutyronitrile and 2,2'-azobis-2,4-dimethylvaleronitrile. Among these radical polymerization initiators, benzoyl peroxide, lauroyl peroxide, 2,2′-azobisisobutyronitrile and the like are preferably used. One or more of these radical polymerization initiators can be used. The amount of the radical polymerization initiator used is, for example, about 0.1 to 5 parts by weight, preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of the polymerizable monomer (I) in the first-stage reaction. If necessary, a surfactant for stabilizing the dispersion of the monomer droplets, for example, anionic surfactants such as sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, and sodium lauryl sulfate; and nonionic surfactants such as polyethylene glycol nonylphenyl ether. An activator may be added. One or more of these surfactants can be used.

The amount of the surfactant used is, for example, 0.05 parts by weight based on 100 parts by weight of the polymerizable monomer (I) in the first reaction.
About 2 parts by weight. If necessary, an aqueous phase polymerization inhibitor such as sodium nitrite may be added. In the step of suspension polymerization of the polymerizable monomer (I) to form rubber-like polymer particles, prior to the initiation of the reaction, the polymerizable monomer (I), a dispersion stabilizer, an oil-soluble radical polymerization initiator, and ion-exchanged water are used. It is preferable to adjust the monomer droplets to a desired size by a shearing force caused by stirring the mixture. In this case, it is preferable to use various dispersing means such as a homomixer, a homodisper, a homogenizer, and a line mixer in order to form fine monomer droplets of 100 μm or less. The size of the monomer droplets can be controlled by adjusting the shearing force by the rotation speed of the dispersion means. The polymerizable monomer dispersion thus prepared is usually heated to the 10-hour half-life temperature of the radical polymerization initiator to carry out the polymerization reaction, whereby a rubbery polymer particle suspension of the first-stage reaction is obtained. For example, when lauroyl peroxide is used, the temperature is raised to 55 ° C. or higher,
When 2'-azobisisobutyronitrile is used, 65
By performing the radical polymerization by raising the temperature to at least ℃, a rubbery polymer particle suspension of the first-stage reaction is obtained. Next, in the second-stage reaction, in the presence of the rubber-like polymer particle suspension obtained in the above-described first-stage reaction, a monomer that forms a glassy polymer is added, and the glass transition temperature has 50 ° C. or more. A glassy polymer is formed. When the glass transition temperature is lower than 50 ° C., fusion between the particles occurs, which may cause deterioration in workability due to blocking or the like or a problem in dispersibility when kneaded into a film. Therefore, the glass transition temperature of the glassy polymer is 50
-140 ° C is preferred, and 60-130 ° C is more preferred.

In the second stage reaction in the present invention, a polymerizable monomer (II) which forms a glassy polymer having a glass transition temperature of 50 ° C. or higher is added to a suspension of the rubbery polymer particles obtained by the first stage reaction. This is a reaction for obtaining a multi-phase structure particle suspension by addition and radical polymerization. Preferred as the polymerizable monomer (II) forming the glassy polymer is
At least one monomer selected from an alkyl (meth) acrylate (d) and an aromatic vinyl monomer (e), and if necessary, a polyfunctional monomer (f) having two or more vinyl groups in the molecule; It is made of a copolymerizable monomer (g). Examples of the alkyl (meth) acrylate (d) include alkyl (meth) acrylates having 1 to 4 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate. Examples of the aromatic vinyl monomer (e) include styrene, vinyl toluene,
α-methylstyrene and the like can be mentioned. The total amount of the monomers (d) and (e) used is usually 50 to 50 in the polymerizable monomer (II) used in the second-stage reaction.
It is 100% by weight, preferably 60 to 100% by weight.
By using the polyfunctional monomer (f) having two or more vinyl groups in the molecule in the second-stage reaction, the dispersibility of the polymer particles may be further improved. As a polyfunctional monomer having two or more vinyl groups in the molecule,
The same thing as the above (b) can be used, and it can be used usually in the range of 0 to 10% by weight, preferably 0 to 5% by weight in the polymerizable monomer (II) of the second stage reaction.

In this second stage reaction, (d)
(G) other copolymerizable monomers copolymerizable therewith with the monomers (e) and (f), for example (meth)
It is also possible to copolymerize vinyl cyanide such as acrylonitrile, vinylidene cyanide, alkyl methacrylate other than methyl methacrylate, alkyl acrylate such as ethyl acrylate and butyl acrylate, and urethane (meth) acrylate. Also, epoxy group,
A monomer having a functional group such as a carboxyl group, a hydroxyl group, or an amino group may be copolymerized. For example, monomers having an epoxy group include glycidyl methacrylate, and monomers having a carboxyl group include methacrylic acid, acrylic acid, maleic acid, and itaconic acid. Examples of the monomer having a hydroxyl group include 2-
Examples include hydroxyethyl methacrylate and 2-hydroxyethyl acrylate. Examples of the monomer having an amino group include diethylaminoethyl methacrylate and diethylaminoethyl acrylate. This other copolymerizable copolymerizable monomer (g)
Of the polymerizable monomer (II) in the second stage reaction
The content is usually 0 to 50% by weight, preferably 0 to 40% by weight.

When the soft film is a soft urethane film, urethane (meth) acrylate is used as another copolymerizable monomer (g) in the polymerizable monomer (II) in the second stage reaction in an amount of from 0.5 to 50%. It is good to use 30% by weight, preferably 1 to 20% by weight. In this case, a monomer other than urethane (meth) acrylate may be used in combination as another copolymerizable monomer (g). Therefore, when other copolymerizable copolymerizable monomer (g) containing urethane (meth) acrylate is used, the amount used is 0.5 to 50% by weight in the polymerizable monomer (II) in the second stage reaction. %, Preferably 1
５０50% by weight. When the matting agent obtained by using urethane (meth) acrylate in the second-stage reaction as described above may be used for a soft urethane film, a more excellent matting effect may be obtained. The time for adding the polymerizable monomer (II) used in the second-stage reaction is desirably the time when the polymerization conversion in the first-stage reaction becomes 90% or more.
If this period is too early, aggregation and fusion may occur between the polymer particles during dehydration and drying of the polymer particles. As a method of adding the polymerizable monomer (II) in the second-stage reaction, an emulsion or suspension is prepared in advance together with the surfactant or dispersion stabilizer described above, and the solution is supplied at once or over a predetermined time. Is preferably used.

In the second stage reaction, a polymerization initiator can be further added. In the case of an oil-soluble radical polymerization initiator, the radical polymerization initiator is dissolved in the polymerizable monomer (II) of the second stage reaction and added. In the case of a water-soluble radical polymerization initiator, it can be separately added in the state of an aqueous solution. As the polymerization initiator that can be used in the second-stage reaction, the above-mentioned oil-soluble radical polymerization initiator can be used, and as the water-soluble radical polymerization initiator, a persulfate-based polymerization such as sodium persulfate and potassium persulfate can be used. Initiator, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2
-Methyl-N- (2-hydroxyethyl) -propionamide] and the like. One or more of these radical polymerization initiators can be used. The amount of the radical polymerization initiator used is, for example, about 0.1 to 10 parts by weight, preferably about 0.05 to 2 parts by weight, per 100 parts by weight of the polymerizable monomer (II) in the second stage reaction. If the amount is too large, new particles or irregularly shaped particles are generated, and it is difficult to form a multiphase structure. The weight ratio of the rubbery polymer in the first-stage reaction to the glassy polymer in the second-stage reaction is usually in the range of 95/5 to 30/70, preferably 90/10 to 50/50.

If the amount of the rubbery polymer in the first-stage reaction is less than this range, sufficient rubber elasticity may not be obtained. On the other hand, if the amount of the rubbery polymer in the first-stage reaction is larger than this range, aggregation and fusion may occur between the polymer particles during dehydration or drying of the polymer particles, and even if the polymer particles are obtained. In addition, workability may be deteriorated due to blocking or the like, or a problem may occur in dispersibility when kneaded into a film. The weight average particle diameter of the multiphase structure particles thus produced is usually 2 to 100 μm.
m, preferably 4 to 80 μm, more preferably 5 to 5 μm.
It is in the range of 0 μm. Those having a weight average particle diameter of 2 μm or less are difficult to produce by this polymerization method, and those having a weight average particle diameter of 100 μm or more have a low matting effect when kneaded into a soft film and have a rough surface. . Examples of a method for isolating the polymer particles obtained after the completion of the reaction include a method of dehydrating with a centrifugal separator or a reduced pressure filter and drying with a reduced pressure dryer or the like, a spray drying method and the like. Before isolation, it is desirable to wash as necessary to remove the dispersion stabilizer and the surfactant attached to the polymer particles. The drying of the polymer particles is preferably performed at normal pressure or reduced pressure at a low temperature of 80 ° C or lower.
If the drying temperature exceeds 80 ° C., some polymer particles may be fused. The obtained polymer particles can be used as they are or, for example, sieved with a mesh of about 100 to 400 to prevent the occurrence of fish eyes during film formation, to give a product. Further, these polymer particles may be further mixed with inorganic fine particles such as fine silica particles, a lubricant, other polymer fine particles, and the like to form a product, if necessary.

The matting agent for a flexible film of the present invention may be, for example, a polyolefin type, a polyester type, a polyamide type,
100 parts by weight of soft resin such as urethane type, acrylic type, styrene type, polyvinyl chloride type, polybutadiene type, polyisoprene type, natural rubber, etc. (resin which is flexible when formed into a film and does not whiten by stretching or bending) 3 to 200 parts by weight, depending on the matting property required,
A matte soft film is obtained by kneading preferably 5 to 120 parts by weight. For the production of the above matte soft film, for example, a soft resin and a matting agent for a soft film are mixed by a mixer, a Henschel mixer, a tumbler, etc., melt-kneaded by a single screw or twin screw extruder, and then subjected to a T-die method or an inflation method. You can do it. In addition to the soft film matting agent of the present invention, if necessary,
Various additives may be used in appropriate amounts. Examples of such additives include a reinforcing material, an inorganic filler, a flame retardant, a release agent, a weather stabilizer, an antioxidant, an antistatic agent, a heat resistance imparting agent, a lubricant, and a surfactant. Can be.

[0019]

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Abbreviations used in the examples and comparative examples are as follows. BA n-butyl acrylate MMA methyl methacrylate EA ethyl acrylate SM styrene EGMA ethylene glycol dimethacrylate ALMA allyl methacrylate BGA 1,4-butylene glycol diacrylate DVB 57% divinylbenzene UA urethane monomethacrylate (2-hydroxyethyl methacrylate: isophorone Diisocyanate
LPO lauroyl peroxide AIBN 2,2'-azobisisobutyronitrile PVA saponification degree 88% polyvinyl alcohol SSS dioctyl sulfosuccinate sodium salt SHC Sodium hydrogen carbonate DIW Deionized water

Example 1 Preparation of matting agent A for soft film and preparation of matte soft film B In a 5 liter container, 2000 g of DIW and 300 g of a 5% PVA aqueous solution were added, and a TK homomixer (Tokusai Kika Kogyo Co., Ltd.) was added. 610 g of BA, 10 g of BGA and 10 g of ALMA 10 in which 10 g of LPO was previously dissolved as a polymerization initiator while stirring at 7000 rpm according to
g of the monomer mixture was added all at once. Further, dispersion treatment was performed for one hour to obtain a monomer dispersion liquid. The vessel was equipped with a stirrer and a reflux condenser, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. After the reaction was continued for 2 hours, sampling was performed from the polymer particle suspension, and the polymerization conversion of the monomer was measured to be 96%. Next, the polymer particle suspension was cooled to 60 ° C., and the second-stage reaction monomer emulsion shown below was added continuously over 10 minutes. Second-stage reaction monomer emulsion MMA 340 g EA 20 g EGMA 10 g AIBN 4 g 1% SSS aqueous solution 100 g DIW 100 g

When the polymerization started and an exothermic peak was observed, the temperature was raised to 80 ° C., and an aging reaction was performed for 3 hours. After cooling the obtained suspension to room temperature, the suspension was dehydrated and washed using a centrifuge, further blast-dried all day and night at 60 ° C., and sieved through a 200-mesh sieve to obtain a gloss for a soft film without aggregation between particles. 950 g of eraser A were obtained. When the weight average particle diameter of the matting agent A for a soft film was measured with a Coulter Multisizer II (manufactured by Coulter Co., Ltd.), it was 8 μm.
Met. The dynamic viscoelasticity of the matting agent A for a soft film was measured, and the glass transition temperature of the rubbery polymer was -4.
0 ° C. and the glass transition temperature of the glassy polymer is 11
3 ° C. Matting agent A1 for soft film obtained
After kneading 00 g and a soft acrylic resin (a copolymer of MMA / BA = 95/5) 900 g at 240 ° C., the mixture was extruded from a T-die to obtain a soft film B having a thickness of 30 μm. The glossiness of the obtained flexible film B is 30 (Nippon Denshoku Industries Co., Ltd.)
GLOS METER (measured at 60 ° -60 °)), and no whitening was observed when the flexible film B was bent. On the other hand, the glossiness of the film to which the matting agent for a flexible film was not added was 140.

Example 2 Preparation of matting agent C for soft film and preparation of matte soft film D In a 5 liter container, 2,000 g of DIW and 300 g of a 5% PVA aqueous solution were added, and a TK homomixer (Tokusai Kika Kogyo Co., Ltd.) was added. While stirring at 5500 rpm according to the method described above, 720 g of BA, 10 g of BGA, and 10 g of ALMA 10 in which 10 g of LPO were previously dissolved as a polymerization initiator.
g of the monomer mixture was added all at once. Further, dispersion treatment was performed for one hour to obtain a monomer dispersion liquid. The polymerization vessel was equipped with a stirrer and a reflux condenser, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. After the reaction was continued for 2 hours, sampling was performed from the polymer particle suspension, and the polymerization conversion of the monomer was measured to be 96%. Next, the polymer particle suspension was cooled to 60 ° C., and the second-stage reaction monomer emulsion shown below was added continuously over 10 minutes. Second-stage reaction monomer emulsion SM 250 g DVB 10 g 1% SSS aqueous solution 100 g 1% SHC aqueous solution 100 g

When the polymerization started and an exothermic peak was observed, the temperature was raised to 80 ° C. and an aging reaction was performed for 3 hours. After cooling the obtained suspension to room temperature, the suspension was dehydrated and washed using a centrifuge, further blast-dried all day and night at 60 ° C., and sieved through a 200-mesh sieve to obtain a gloss for a soft film without aggregation between particles. 960 g of eraser C were obtained. When the weight average particle diameter of the matting agent C for a soft film was measured with a Coulter Multisizer II (manufactured by Coulter Co., Ltd.), it was 13 μm.
m. The dynamic viscoelasticity of the matting agent C for a soft film was measured, and the glass transition temperature of the rubbery polymer was-
40 ° C. and the glass transition temperature of the glassy polymer is 1
20 ° C. Matting agent C for soft film obtained
200g and soft acrylic resin (MMA / BA = 95/5
After kneading 800 g at 240 ° C., the mixture was extruded from a T-die to obtain a soft film D having a thickness of 50 μm. The glossiness of the obtained soft film D was 20 (GLOSSMETER manufactured by Nippon Denshoku Industries Co., Ltd. (measured at 60 ° -60 °)), and no whitening was observed when bending the soft film D. On the other hand, the glossiness of the film to which the matting agent for a flexible film was not added was 140.

Example 3 Preparation of matting agent E for soft film and preparation of matte soft film F In a 5 liter container, 1950 g of DIW and 175 g of a 5% aqueous solution of PVA were added, and a TK homomixer (Tokusai Kika Kogyo Co., Ltd.) was added. While stirring at 4400 rpm according to (1), a monomer mixture of 450 g of BA, 148 g of MMA, and 2 g of BGA, in which 8 g of LPO was previously dissolved as a polymerization initiator, was added all at once. Further, dispersion treatment was performed for one hour to obtain a monomer dispersion liquid. The polymerization vessel was equipped with a stirrer and a reflux condenser, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. After the reaction was continued for 2 hours, sampling was performed from the polymer particle suspension, and the polymerization conversion of the monomer was measured to be 97%. Next, the polymer particle suspension was cooled to 60 ° C., and the second-stage reaction monomer emulsion shown below was added continuously over 10 minutes. Second-stage reaction monomer emulsion MMA 360 g EA 20 g BGA 10 g UA 10 g AIBN 8 g 1% SSS aqueous solution 125 g 1% SHC aqueous solution 125 g DIW 125 g

When the polymerization started and an exothermic peak was observed, the temperature was raised to 80 ° C. and an aging reaction was performed for 3 hours. After cooling the obtained suspension to room temperature, the suspension was dehydrated and washed using a centrifuge, further blast-dried all day and night at 60 ° C., and sieved through a 200-mesh sieve to obtain a gloss for a soft film without aggregation between particles. 960 g of eraser E were obtained. When the weight average particle diameter of the matting agent E for a soft film was measured with a Coulter Multisizer II (manufactured by Coulter Co., Ltd.),
m. Further, the dynamic viscoelasticity of the matting agent E for a flexible film shows that the glass transition temperature of the rubbery polymer is −
2 ° C., and the glass transition temperature of the glassy polymer is 11
8 ° C. Matting agent E5 for soft film obtained
00g and thermoplastic polyurethane resin (Elastoran C8
5A Takeda Bird Dish Urethane Industry Co., Ltd.) 50
After kneading 0 g at 230 ° C., extruded from a T-die,
A flexible film F of 00 μm was obtained. The glossiness of the obtained flexible film F is 1 (GLOSS manufactured by Nippon Denshoku Industries Co., Ltd.).
METER (measured at 60 ° -60 °)), and no whitening was observed during stretching or bending. On the other hand, the glossiness of the film to which no matting agent for a flexible film was added was 140.

Example 4 Preparation of matting agent G for soft film and preparation of matte soft film H In a 5 liter container, 2,000 g of DIW and 200 g of a 5% aqueous solution of PVA were added, and TK homomixer (Tokusai Kika Kogyo Co., Ltd.) was added. 530 g of BA, 147.5 g of MMA, BGA in which 8 g of LPO was previously dissolved as a polymerization initiator while stirring at 6000 rpm according to
A monomer mixture of 2.5 g was added all at once. Further, dispersion treatment was performed for one hour to obtain a monomer dispersion liquid. The polymerization vessel was equipped with a stirrer and a reflux condenser, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. After the reaction was carried out for 2 hours as it was, sampling was performed from the polymer particle suspension, and the polymerization conversion of the monomer was measured.
%Met. Next, the polymer particle suspension was cooled to 60 ° C., and the second-stage reaction monomer emulsion shown below was added continuously over 10 minutes. Second-stage reaction monomer emulsion MMA 246 g EA 16 g BGA 10 g UA 48 g AIBN 6.4 g 1% SSS aqueous solution 100 g 1% SHC aqueous solution 100 g DIW 100 g

When the polymerization started and an exothermic peak was observed, the temperature was raised to 80 ° C. and an aging reaction was performed for 3 hours. After cooling the obtained suspension to room temperature, the suspension was dehydrated and washed using a centrifuge, further blast-dried all day and night at 60 ° C., and sieved through a 200-mesh sieve to obtain a gloss for a soft film without aggregation between particles. 960 g of eraser G were obtained. When the weight average particle diameter of the matting agent G for a soft film was measured with a Coulter Multisizer II (manufactured by Coulter Co., Ltd.),
m. The dynamic viscoelasticity of the delustering agent G for a flexible film was measured, and the glass transition temperature of the rubbery polymer was −
4 ° C. and the glass transition temperature of the glassy polymer is 11
It was 0 ° C. Matting agent G5 for soft film obtained
00g and thermoplastic polyurethane resin (Elastoran C9
5A Takeda Bird Dish Urethane Industry Co., Ltd.) 50
After kneading 0 g at 230 ° C., extruded from a T-die,
A flexible film H of 00 μm was obtained. The glossiness of the obtained soft film H is 1 (GLOSS manufactured by Nippon Denshoku Industries Co., Ltd.).
METER (measured at 60 ° -60 °)), and no whitening was observed during stretching or bending. On the other hand, the glossiness of the film to which no matting agent for a flexible film was added was 140.

Comparative Example 1 Preparation of Polymer Particles I and Preparation of Flexible Film J In a 5 liter container, 2,200 g of DIW and 300 g of a 5% aqueous solution of PVA were added, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used at 7,500 rpm. While stirring, a monomer mixture composed of 950 g of MMA and 50 g of EGMA in which 10 g of LPO was previously dissolved as a polymerization initiator was added all at once. Further, dispersion treatment was performed for one hour to obtain a monomer dispersion liquid. A stirrer and a reflux condenser were attached to the polymerization vessel, and the mixture was stirred for 7 minutes under a nitrogen stream.
The temperature was raised to 0 ° C. When the polymerization started and an exothermic peak was observed, the temperature was raised to 80 ° C. and the aging reaction was performed for 4 hours. The obtained suspension was cooled to room temperature, dehydrated and washed using a centrifugal machine, further blast-dried at 60 ° C all day and night, and passed through a 200-mesh sieve, whereby polymer particles I having no aggregation between particles were obtained. 960 g were obtained. The weight average particle diameter of the polymer particles I measured by Coulter Multisizer II (manufactured by Coulter KK) was 8 μm. Also,
The dynamic viscoelasticity of the polymer particles I indicates that the polymer
The glass transition temperature of Particle I was 120 ° C. 100 g of the obtained polymer particles I and a soft acrylic resin (MMA
After kneading 900 g at 240 ° C., the mixture was extruded from a T-die to obtain a soft film J having a thickness of 30 μm. The glossiness of the obtained soft film J is 30.
(GLOSMETER (60 manufactured by Nippon Denshoku Industries Co., Ltd.)
{-60} measurement), but the soft film J lost its flexibility and was easily whitened by bending.

Comparative Example 2 Preparation of Polymer Particles K and Preparation of Flexible Film L In a 5 liter container, 2,200 g of DIW and 300 g of a 5% aqueous solution of PVA were added, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used at 7,500 rpm. While stirring, 610 g of BA, 340 g of MMA, and EA 20 in which 10 g of LPO were previously dissolved as a polymerization initiator.
g, BGA 10g, EGMA 10g, ALMA 10
g of the monomer mixture was added all at once. Further, a dispersion treatment was performed for one hour to prepare a monomer dispersion liquid. The polymerization vessel was equipped with a stirrer and a reflux condenser, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. When the polymerization started and an exothermic peak was observed, the temperature was raised to 80 ° C. and the aging reaction was performed for 4 hours. Thereafter, the mixture was cooled to room temperature to obtain a suspension of polymer particles. The weight average particle diameter of this suspension was measured with a Coulter Multisizer II (manufactured by Coulter Corp.) and found to be 8 μm. When the suspension of the polymer particles is dehydrated and washed using a centrifuge, the aggregation between the polymer particles is intense.
(Polymer mass) was obtained. In addition, polymer particles K
As a result of measurement of dynamic viscoelasticity, the glass transition temperature of the polymer particles K was 2 ° C. 100 g of the obtained polymer particles K (polymer mass) and a soft acrylic resin (MMA /
900 g of a copolymer (BA = 95/5) was kneaded at 240 ° C., and extruded from a T-die to obtain a soft film L having a thickness of 30 μm. The glossiness of the obtained soft film L was 50 (GLOSS METER manufactured by Nippon Denshoku Industries Co., Ltd. (measured at 60 ° -60 °)). In this case, since the particles did not disperse to the primary particles, the surface was rough.

[0030]

When the matting agent for a soft film of the present invention is kneaded with a soft resin, polymer particles are dispersed to primary particles, and a soft film having excellent transparency and excellent matting properties can be obtained. . The matting agent for a flexible film of the present invention does not impair the flexibility, toughness, and texture of the flexible film, and does not cause whitening when the film is bent or stretched.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Shinji Tachibana 2-17-85, Jusanhoncho, Yodogawa-ku, Osaka-shi, Osaka Inside the Chemicals Company Takeda Pharmaceutical Co., Ltd. (72) Inventor Hiroshi Takeuchi Osaka, Osaka 2-17-85 Jusanhoncho, Yodogawa-ku, Tokyo Takeda Pharmaceutical Co., Ltd., Chemicals Company (72) Inventor, Shunsaku Tanaka 960 Shimo-Kokura, Kashiwara-cho, Hikami-gun, Hyogo

Claims (10)

[Claims] 1. A first-stage reaction for forming a rubber-like polymer having a glass transition temperature of 20 ° C. or lower by radical polymerization of a polymerizable monomer (I) for forming a rubber-like polymer, followed by a first-stage reaction for forming a rubber-like polymer having a glass transition temperature of 50 ° C. or higher. A matting agent for a soft film containing multi-phase structured particles produced by a second-stage reaction in which a polymerizable monomer (II) for forming a glassy polymer is added to perform radical polymerization. 2. The matting agent for a flexible film according to claim 1, wherein the radical polymerization in the first-stage reaction is suspension polymerization. 3. The multi-phase structure particles having a weight average particle diameter of 2 to 10.
The matting agent for a flexible film according to claim 1, which has a thickness of 0 µm. 4. The polymerizable monomer (I) forming the rubbery polymer is an alkyl (meth) acrylate (a) 50 to 50.
99.9% by weight, 0.1 to 20% by weight of a polyfunctional monomer (b) having two or more vinyl groups in a molecule and 0 to 49.9% by weight of another copolymerizable monomer (c). The matting agent for a flexible film according to claim 1, which is a monomer mixture. 5. The polymerizable monomer (II) which forms a glassy polymer is 50 to 100% by weight of at least one monomer selected from an alkyl (meth) acrylate (d) and an aromatic vinyl monomer (e). Multifunctional monomer (f) having two or more vinyl groups in the molecule (f) 0 to 10
% By weight and other copolymerizable monomers (g) 0 to 50
The matting agent for a flexible film according to claim 1, which is a monomer or a monomer mixture consisting of wt%. 6. The polymerizable monomer (II) forming the glassy polymer is at least one monomer selected from the group consisting of alkyl (meth) acrylate (d) and aromatic vinyl monomer (e) in an amount of 50 to 99.5% by weight. %, A polyfunctional monomer having two or more vinyl groups in the molecule (f) 0 to 1
0% by weight and urethane (meth) acrylate 0.5 to
Other copolymerizable monomers (g) containing 30% by weight.
The matting agent for a flexible film according to claim 5, which is a monomer mixture comprising 5 to 50% by weight, and wherein the flexible film is a flexible urethane film. 7. The matting agent for a flexible film according to claim 1, wherein the weight ratio of the rubbery polymer to the glassy polymer is from 95/5 to 30/70. 8. The second-stage reaction is carried out by adding an emulsion containing a polymerizable monomer (II) forming a glassy polymer and a surfactant to the first-stage reaction solution and absorbing or adhering the first-stage particles to radical polymerization. The matting agent for a flexible film according to claim 1, wherein 9. A matte soft film comprising a soft film containing the matting agent for a soft film according to any one of claims 1 to 8. 10. The matte soft film according to claim 9, wherein the soft film matting agent is contained in an amount of 3 to 200 parts by weight based on 100 parts by weight of the soft film.