JP2003335912A - Acrylic resin composition for coextrusion molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an acrylic resin composition for coextrusion molding to provide a coextruded product having good impact strength in a low temperature atmosphere, good weatherability and moldability. <P>SOLUTION: The acrylic resin for coextrusion molding comprises 100 pt.mass thermoplastic resin composition and 1-20 pt.mass crosslinked particles comprising an alkyl (meth)acrylate as a main ingredient and having 1-20 μm average particle size. The thermoplastic resin composition comprises a graft copolymer (X) and a (co)polymer (Y) comprising the alkyl (meth)acrylate as a main ingredient. The graft copolymer (X) is obtained by graft polymerizing one or more species of monomers or a monomer mixture (B) selected from aromatic alkenyls, vinyl cyanide compounds and alkyl(meth)acrylates onto a complex rubber (A) consisting of a polyorganosiloxane (a-1) and a polyalkyl acrylate (a-2). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to weather resistance, moldability,
The present invention relates to an acrylic resin composition for co-extrusion molding for obtaining a laminated molded product excellent in pigment coloring and impact resistance under a low temperature environment, and a laminated molded product using the same.

[0002]

2. Description of the Related Art Conventionally, for products with high designability such as window frames, bench materials, and decorative columns, vinyl chloride resin, which has good workability, has been used as a material in terms of the degree of freedom of the surface and the shape. It is used. When this processed product of vinyl chloride resin is used outdoors, there have been problems such as surface whitening, lowering of gloss and yellowing due to poor weather resistance of the vinyl chloride resin. As a method for improving this problem, a technique of coextrusion molding a resin containing an acrylic resin as a main component with a vinyl chloride resin to form an acrylic resin layer having excellent weather resistance on the surface of a molded article has been conventionally known. ing.

In a method for producing a laminated molded article by co-extruding an acrylic resin with a vinyl chloride resin, the acrylic resin layer is made uniform when the fluidity of the acrylic resin is increased and the shape is fixed with a sizing die. It is important that the vinyl chloride resin is laminated with a certain thickness. Further, stains and the like on the die plate deteriorate the design of the co-extrusion molded product, so suppressing this is an important issue in the molding process.

In addition, in a laminated molded article having an acrylic resin as a surface layer, due to the brittleness of the acrylic resin layer having relatively low impact resistance, the impact resistance when an impact is applied from the acrylic resin layer side of the laminated molded article. Lowness can often be a problem. In particular, regarding a window frame profile that uses a laminated molded product as a constituent material of an opening of a building, the Charpy impact value described in JIS K6785 is 12.7 kJ / m ² or more (23
° C.), it is necessary to satisfy the criteria of 4.97kJ / m ² or more (-10 ° C.) and low temperature falling weight strength.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
In the publication, an acrylic copolymer (I) composed of methacrylic acid alkyl ester and acrylic acid alkyl ester and having a specific reduced viscosity and a multilayer structure polymer (II) containing an acrylic resin as a main component are mixed. The average particle size of which the main component is methyl methacrylate relative to the resin composition
Described is an acrylic resin composition in which crosslinked fine particles (III) having a particle size of up to 20 μm are mixed. When this acrylic resin composition is profile extruded with a vinyl chloride resin, stain adhesion (plate-out) occurs on the sizing die. However, it is said that it exhibits good moldability and good impact resistance.

However, although a laminated molded article using this acrylic resin composition has good moldability, it lacks impact resistance, especially in a low temperature atmosphere. When used as a profile, JIS K
It was difficult to satisfy the performance of the impact test based on 6785. In addition, the laminated molded article having such a poor impact resistance is limited in its use.

On the other hand, for the purpose of improving the impact resistance of an acrylic resin / vinyl chloride resin coextrusion molded article,
It is disclosed in JP-A-5-339459 and JP-A-6-2859 that a polybutadiene rubber is further contained in an acrylic resin composition containing an acrylic graft copolymer.
No. 43, it is stated that a vinyl chloride resin coextrusion molded article using the same exhibits good impact resistance and moldability.

However, although the coextrusion molded article using this acrylic resin composition has a good impact resistance, it contains a polybutadiene-based rubber having a poor light stability, so that it has a weather resistance and especially an acrylic resin layer. Laminated products that are lightly colored have poor yellowing resistance to sunlight and rainfall, and are difficult to use for outdoor building materials such as window frame profiles and outer wall materials that require a particularly high level of weather resistance. Met.

An acrylic resin composition having improved impact resistance without impairing weather resistance is disclosed in JP-A-11-19.
9642 and JP-A-2000-186182 disclose a composite rubber system in which a composite rubber composed of a polyorganosiloxane and a polyalkyl acrylate is graft-polymerized with a monomer mixture composed of an aromatic alkenyl compound and a vinyl cyanide compound. A resin composition comprising a graft copolymer and an acrylic resin is disclosed.

However, Japanese Patent Laid-Open No. 11-199642
JP-A-2000-186182 and JP-A-2000-186182 disclose
Although it is suggested to improve the impact resistance of the acrylic resin composition itself, particularly the impact resistance of the injection-molded resin molded product, a specific method used for coextrusion molding with a vinyl chloride resin, or There is no suggestion of any specific method for obtaining a coextrusion molded article having good moldability and impact resistance, and further, the use of the coextrusion molded article as a window frame profile. In addition, the resin compositions described in the examples of these publications had poor appearance due to plate-out during coextrusion with a vinyl chloride resin, and it was difficult to perform good coextrusion. Here, the plate-out means that a resin composition to be co-extruded, a decomposed product such as an additive compounded, a poor dispersion of a pigment or the like adheres to a sizing die, and a co-extruded product is obtained. Is a phenomenon that impairs the design.

Therefore, the object of the present invention is JIS K67.
Acrylic resin composition for coextrusion molding for obtaining a coextrusion molded article having good impact resistance in a low temperature atmosphere satisfying the performance of an impact test according to 85, good weather resistance and moldability, and It is to provide a laminated molded product using the same.

[0012]

Means for Solving the Problems The inventors of the present invention have made earnest studies on an acrylic resin composition which is coextruded with a vinyl chloride resin, and as a result, a specific acrylic copolymer and a composite rubber-based graft copolymer have been obtained. , And by using an acrylic resin composition containing crosslinked fine particles for coextrusion molding, it was found that a laminated molded article having good impact resistance in a low temperature atmosphere and good moldability can be obtained, Arrived

That is, the acrylic resin composition for coextrusion molding of the present invention is obtained by adding aromatic alkenyl and cyanide to a composite rubber (A) composed of polyorganosiloxane (a-1) and polyalkyl acrylate (a-2). A graft copolymer (X) obtained by graft-polymerizing at least one monomer or a monomer mixture (B) selected from a vinyl compound and an alkyl (meth) acrylate, and an alkyl (meth) acrylate as a main component. Alkyl (meth) acrylate is the main component with respect to 100 parts by mass of the thermoplastic resin composition comprising the (co) polymer (Y) as a component and the graft copolymer (X) and (co) polymer (Y). 1 to 20 parts by mass of crosslinked fine particles having an average particle diameter of 1 to 20 μm as a component are contained.

Further, the (co) polymer (Y) containing an alkyl (meth) acrylate as a main component is prepared according to JIS K7210.
Melt mass flow rate (MFR) measured according to
Is preferably in the range of 15 to 25 g / 10 min. Further, the acrylic resin composition for coextrusion molding of the present invention is preferably colored by using a colorant masterbatch using an acrylic resin as a binder.

The laminated molded article of the present invention is characterized in that it is obtained by co-extruding and molding the acrylic resin composition for co-extrusion molding of the present invention and a vinyl chloride resin. Further, the profile for a window frame of the present invention is characterized by comprising the laminated molded article of the present invention.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. <Composite rubber (A)> The polyorganosiloxane (a-1) constituting the composite rubber (A) according to the present invention is not particularly limited, but preferably a polypolymer containing a vinyl polymerizable functional group. It is an organosiloxane. More preferably, the vinyl-polymerizable functional group-containing siloxane unit 0.3
~ 3 mol% and dimethylsiloxane units 97-99.
The polyorganosiloxane comprises 7 mol% and further has 1 mol% or less of silicon atoms having 3 or more siloxane bonds with respect to all silicon atoms in the polydimethylsiloxane.

When the content of the vinyl-polymerizable functional group-containing siloxane unit in the polyorganosiloxane (a-1) is less than 0.3 mol%, the compounding with the polyalkyl acrylate (a-2) becomes insufficient, resulting in an acrylic resin composition. The surface appearance of the coextrusion molded product using the product deteriorates. In addition, the vinyl-polymerizable functional group-containing siloxane unit in the polyorganosiloxane (a-1) exceeds 3 mol%, or the silicon atom having three or more siloxane bonds is 1 with respect to all the silicon atoms in the polyorganosiloxane. When it exceeds mol%, the impact resistance of the acrylic resin composition tends to be low. Furthermore, considering both the impact resistance and the appearance of molding of the acrylic resin composition, the vinyl-polymerizable functional group-containing siloxane unit in the polyorganosiloxane (a-1) is preferably 0.5 to 2
Mol%, and more preferably 0.5 to 1 mol%.

The method for producing the polyorganosiloxane (a-1) is not particularly limited, but an emulsion polymerization method is preferable. As the emulsion polymerization method, for example, a mixture of dimethyl siloxane and a vinyl-polymerizable functional group-containing siloxane, or a mixture containing a siloxane-based cross-linking agent, if necessary, is emulsified with an emulsifier and water to form a latex,
After homogenizing this latex using a homomixer that atomizes it with shearing force due to high-speed rotation or a homogenizer that atomizes with a jet output from a high-pressure generator, a unit amount in the latex at high temperature using an acid catalyst One method is to polymerize the body and then neutralize the acid with an alkaline substance.

As a method of adding an acid catalyst used for polymerization,
There are a method of mixing with a siloxane mixture, an emulsifier and water, and a method of dropping a latex in which the siloxane mixture is made into fine particles into a hot acid aqueous solution at a constant rate. Considering this, a method in which a latex in which the siloxane mixture is finely divided is dropped into a hot acid aqueous solution at a constant rate is preferable.

Examples of the dimethylsiloxane used for producing the polyorganosiloxane (a-1) include a dimethylsiloxane cyclic compound having a 3-membered ring or more, and a 3-membered to 7-membered ring is preferable. Specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc. These may be used alone or in combination of two or more.

The vinyl-polymerizable functional group-containing siloxane contains a vinyl-polymerizable functional group and can be bonded to dimethylsiloxane through a siloxane bond.
Considering the reactivity with dimethylsiloxane, various alkoxysilane compounds having a vinyl polymerizable functional group are preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane and methacryloyloxysiloxanes such as rusilane, vinyl siloxanes such as tetra δ-methacryloyloxybutyldiethoxymethymethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane and γ-mercaptopropyldimethoxy. Methylsilane,
Examples include mercaptosiloxanes such as γ-mercaptopropyltrimethoxysilane. These vinyl-polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more kinds.

As the siloxane-based crosslinking agent, a trifunctional or tetrafunctional silane-based crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane or tetrabutoxysilane is used. .

Further, polyorganosiloxane (a-1)
As the emulsifier used in the production of, an anionic emulsifier is preferable, sodium alkylbenzenesulfonate,
An emulsifier selected from sodium polyoxyethylene nonylphenyl ether sulfate and the like is used. In particular, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable. These emulsifiers are siloxane mixtures 1
It is used in the range of about 0.05 to 5 parts by mass with respect to 00 parts by mass. When the amount used is small, the dispersion state becomes unstable, and it becomes impossible to maintain the emulsified state with a fine particle size. Further, if the amount used is large, coloring of the resin composition molded product due to the emulsifier becomes severe.

Examples of the method of mixing the siloxane mixture, the emulsifier, water and / or the acid catalyst include high-speed stirring, high-pressure emulsifying equipment such as a homogenizer, and the like. Among them, the method using a homogenizer is polyorgano. This is a preferred method because the particle size distribution of the siloxane latex becomes smaller.

Examples of the acid catalyst used for producing the polyorganosiloxane (a-1) include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid and aliphatic substituted naphthalenesulfonic acid, and sulfuric acid, hydrochloric acid, nitric acid and the like. Mineral acids are mentioned. These acid catalysts may be used alone or in combination of two or more. Among these, aliphatic-substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable, because it is also excellent in stabilizing the polyorganosiloxane latex. When n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, coloring of the resin composition due to the emulsifier component of the polyorganosiloxane latex can be reduced.

The polymerization temperature during the production of the polyorganosiloxane (a-1) is preferably 50 ° C. or higher, more preferably 80 ° C. or higher. Polyorganosiloxane (a
The polymerization time in the production of -1) is 2 hours or more, more preferably 5 hours or more when the acid catalyst is mixed with the siloxane mixture, the emulsifier and water to form fine particles, and more preferably 5 hours or more. In the method of dropping the finely divided latex, after the dropping of the latex is completed,
It is preferable to hold it for about 1 hour. The termination of the polymerization can be performed by cooling the reaction solution and further neutralizing the latex with an alkaline substance such as caustic soda, caustic potash and sodium carbonate.

After adding the alkyl acrylate and the polyfunctional alkyl (meth) acrylate to the polyorganosiloxane latex produced in this way and impregnating these with the polyorganosiloxane in the latex,
By polymerizing the impregnated monomer, a composite rubber (A) composed of the polyorganosiloxane (a-1) and the polyalkyl acrylate (a-2) can be obtained.

The amount of polyorganosiloxane (a-1) in the composite rubber (A) according to the present invention is not particularly limited, but is preferably 1 to 20% by mass. When the polyorganosiloxane (a-1) is less than 1% by mass, the impact resistance of the acrylic resin composition is low because the amount of the polyorganosiloxane (a-1) is small, and when it exceeds 20% by mass, the acrylic resin composition is The pigment coloring property of the product decreases. In consideration of both impact resistance and pigment colorability of the acrylic resin composition, the amount of polyorganosiloxane (a-1) in the composite rubber (A) is preferably 6 to 20% by mass, more preferably 10%.
Is about 20% by mass.

The polyalkyl acrylate (a-2) is
It is composed of an alkyl acrylate and a polyfunctional alkyl (meth) acrylate. Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. These can be used alone or in combination of two or more. Of these, it is preferable to use n-butyl acrylate.

As the polyfunctional alkyl (meth) acrylate, for example, allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate,
Examples thereof include triallyl cyanurate and triallyl isocyanurate. These can be used alone or in combination of two or more. An example of a preferred polyfunctional alkyl (meth) acrylate is a combination of allyl methacrylate and 1,3-butylene glycol dimethacrylate. The amount of the polyfunctional alkyl (meth) acrylate used is 0.1 to 0.1 in the component composed of the alkyl acrylate and the polyfunctional alkyl (meth) acrylate.
It is 20% by mass, preferably 0.2 to 5% by mass, more preferably 0.2 to 1% by mass.

The composite rubber (A) composed of the polyorganosiloxane (a-1) and the polyalkyl acrylate (a-2) is prepared by adding the above-mentioned alkyl acrylate and polyfunctional alkyl (a) into the latex of the polyorganosiloxane (a-1). It can be prepared by adding a mixture of (meth) acrylate and polymerizing it by allowing a usual radical polymerization initiator to act. As a method of adding the acrylate component, a method of mixing with the latex of the polyorganosiloxane (a-1) at once and a method of adding the polyorganosiloxane (a-
There is a method of dropping the latex in 1) at a constant rate. Of these, considering the impact resistance of the acrylic resin composition, a method of mixing with the latex of the polyorganosiloxane (a-1) at once is preferable.

As the radical polymerization initiator used for the polymerization, a peroxide, an azo type initiator, or a redox type initiator in which an oxidizing agent and a reducing agent are combined is used. Among these, a redox type initiator is preferable, and a sulfoxylate type initiator in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, and hydroperoxide are combined is particularly preferable.

The weight average particle diameter of the composite rubber (A) is 0.
It is preferably 08 to 0.16 μm. When the weight average particle diameter is less than 0.08 μm, the impact resistance of the acrylic resin composition tends to be low, and when it exceeds 0.16 μm, the pigment coloring property of the acrylic resin composition tends to be low. It is in. A more preferable weight average particle diameter is 0.
It is 1 to 0.15 μm.

<Graft Copolymer (X)> The graft copolymer (X) according to the present invention is prepared by subjecting the composite rubber (A) produced by emulsion polymerization to the aromatic alkenyl,
It is produced by graft-copolymerizing at least one monomer or monomer mixture (B) selected from vinyl cyanide compounds and alkyl (meth) acrylates.

Aromatic alkenyl compounds used for graft copolymerization include styrene and α-methylstyrene, vinyl cyanide compounds include acrylonitrile, and alkyl (meth) acrylates include methyl acrylate and ethyl acrylate. , Alkyl acrylates such as propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate; and alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. Of these, styrene and acrylonitrile are preferably used in consideration of impact resistance and thermal stability of the acrylic resin composition.

The amount of the monomer used in the graft copolymerization is 65 to 85% by mass of the aromatic alkenyl compound, 15 to 35% by mass of the vinyl cyanide compound, and other monomers copolymerizable with these compounds. ~ 15% by mass (total 100
Mass%) is preferable. If it deviates from these amounts, the impact resistance of the acrylic resin composition may be impaired. Further, various chain transfer agents for adjusting the molecular weight and the graft ratio of the graft polymer can be added to the monomer mixture used in the graft copolymerization.

Graft copolymerization is carried out by adding at least one monomer or monomer mixture (B) selected from aromatic alkenyl, vinyl cyanide compound and alkyl (meth) acrylate to the latex of the composite rubber (A). In addition, the radical polymerization technique may be used in one step or in multiple steps. Considering impact resistance and pigment coloring of the resulting acrylic resin composition containing the graft copolymer (X), the step should be performed in two or more steps. Is preferred. The amount of the monomer or monomer mixture (B) used in the graft copolymerization is 80 to 140 with respect to 100 parts by mass of the composite rubber (A).
Parts by mass, preferably 100 to 120 parts by mass. At the time of graft copolymerization, all the monomer mixture may not be a graft component and may be present as a partial homopolymer.

In the graft copolymerization, an emulsifier can be added to stabilize the polymerized latex. The emulsifier is not particularly limited, but preferable examples of the emulsifier are a cationic emulsifier, an anionic emulsifier and a nonionic emulsifier, and more preferable examples are a sulfonate emulsifier or a sulfate emulsifier and a carboxylate. It is a combination with an emulsifier. After the graft copolymerization is completed, the latex is put into hot water in which metal salts such as calcium acetate and aluminum sulfate are dissolved,
By salting out and coagulating, the graft copolymer (X) can be separated and recovered.

<(Co) polymer (Y)> The (co) polymer (Y) having an alkyl (meth) acrylate as a main component according to the present invention means an alkyl (meth) acrylate unit as a main constituent component. It is a polymer or copolymer. Here, the alkyl (meth) acrylate refers to alkyl acrylate or alkyl methacrylate.

As the acrylic (meth) acrylate component constituting the (co) polymer (Y), methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n
-Alkyl acrylates such as octyl acrylate,
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate can be mentioned.

The (co) polymer (Y) containing an alkyl (meth) acrylate as a main component preferably contains 80% by mass or more of methyl methacrylate units, and
It may contain an alkyl acrylate unit other than methyl methacrylate or a vinyl-based monomer unit in an amount of not more than mass%. Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and n.
Examples of the vinyl-based monomer include styrene, α-substituted styrene, nucleus-substituted styrene and its derivatives such as α-methylstyrene, chlorostyrene and vinyltoluene.

The (co) polymer (Y) containing alkyl (meth) acrylate as a main component, which constitutes the acrylic resin composition for coextrusion molding of the present invention, has a melt mass flow rate (MFR) measured according to JIS K7210. ) Value is 1
It is preferably 5 to 25 g / 10 min. Melt mass flow rate (MFR) value is 15g / 10min
When it is less than 25 g, the thickness of the acrylic resin layer tends to be nonuniform when coextruded, and when it exceeds 25 g / 10 min, the impact resistance tends to decrease. More preferable melt mass flow rate (MFR) value is 17 to 23.
It is g / 10min. The value of the melt mass flow rate (MFR) of the (co) polymer (Y) containing alkyl (meth) acrylate as a main component can be controlled by adjusting the glass transition temperature or the molecular weight.

The proportion of the (co) polymer (Y) containing alkyl (meth) acrylate as a main component in the acrylic resin composition for coextrusion molding of the present invention is preferably 20 to 85% by mass. When it is less than 20% by mass, the moldability when coextruding with a vinyl chloride resin tends to deteriorate, and when it exceeds 85% by mass, the impact resistance tends to decrease. More preferably, it is 30 to 70 mass%.

<Crosslinked Fine Particles> The crosslinked fine particles constituting the acrylic resin composition for coextrusion molding of the present invention are spherical polymer fine particles having a crosslinked structure. Considering the weather resistance and colorability of the coextrusion molded article using the acrylic resin composition for coextrusion molding of the present invention, as the crosslinked fine particles,
Crosslinked acrylic fine particles are most preferred. Specifically, as the structural unit, those having an acrylic acid alkyl ester or a methacrylic acid alkyl ester as a main component are preferable,
Further, a combination of these with an aromatic vinyl compound such as styrene or substituted styrene is also preferable.

As the crosslinking agent, a polyfunctional monomer such as divinylbenzene, trivinylbenzene or alkylene glycol diacrylate is used. These may be used alone or in combination of two or more. The amount of the cross-linking agent used is based on the total monomer components including the cross-linking agent.
It is 2 to 50% by mass, preferably 5 to 20% by mass. It is preferable that the crosslinked fine particles do not lose their shape in the heat or kneading during coextrusion molding or have a great influence on the fluidity of the base resin. For that purpose, the amount of the crosslinking agent used is increased and the degree of crosslinking is increased. Is desirable.

The average particle size of the crosslinked fine particles is 1 to 20 μm.
It is necessary to make it m. If the average particle size is less than 1 μm, the effect of suppressing plate-out is small, while 20 μm
When it exceeds, the dispersion becomes difficult and the uniformity of the appearance deteriorates.

The crosslinked fine particles are the graft copolymer (X).
And a (co) polymer (Y) containing alkyl (meth) acrylate as a main component.
1 to 20 parts by weight, preferably 3 to 10 parts by weight
Parts by mass are added. If the addition amount of the crosslinked fine particles is less than 1 part by mass, plate out is not eliminated, while if it exceeds 20 parts by mass, the characteristics of the base resin composition such as fluidity and impact resistance are impaired, and the surface The matte state becomes too strong. Here, as the crosslinked acrylic fine particles which are the most preferable examples of the crosslinked fine particles constituting the acrylic resin composition for coextrusion molding of the present invention, Sekisui Chemical Co., Ltd.
Commercially available as MBXR-8N.

<Other Components of Acrylic Resin Composition> The acrylic resin composition for coextrusion molding of the present invention can be colored. Preferable colorants for coloring include a colorant masterbatch in which an acrylic resin is used as a binder and a colorant component is mixed therein, and a dry color in which a dispersant and a colorant component are mixed. Also,
The crosslinked fine particles themselves may be colored.

The colorant masterbatch referred to here is a mixture of a resin and a colorant component at a high concentration, and examples of the form include pellets and soft plate-like ones. Further, the resin serving as the binder is not particularly limited, but is preferably the same as or similar to the resin to be molded, for example, the main component is an alkyl (meth) acrylate constituting the acrylic resin composition for coextrusion molding of the present invention. (Co) polymer (Y) and the like. This colorant masterbatch can be obtained, for example, by kneading a resin and a colorant component by a known melt-kneading method, and freeze-milling. When melt-kneading, an extruder, a Banbury mixer, a pressure kneader, a kneader such as a roll, or the like may be used.

On the other hand, the dry color means a dispersible powder colorant, which is a colorant mechanically finely powdered by adding an appropriate dispersant. Examples of preferable dispersants include calcium stearate and magnesium stearate, and these may be used alone or in combination.

As a coloring agent for coloring the acrylic resin composition for co-extrusion molding of the present invention, a coloring agent masterbatch is preferable from the viewpoint of suppressing plate-out of the coloring agent.
Examples of the colorant component include inorganic pigments such as zinc ferrite, iron oxide and titanium oxide, and organic pigments such as isoindolinone type, phthalocyanine type and perylene type pigments.

In the acrylic resin composition for coextrusion molding of the present invention, if necessary, a stabilizer, a lubricant, a processing aid, a plasticizer,
An impact resistance auxiliary agent, a foaming agent, a filler, an antibacterial agent, an antifungal agent, a foaming agent, a release agent, an antistatic agent, a colorant, a matting agent, an ultraviolet absorber, a flame retardant and the like can be added. Particularly, from the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance.

The acrylic resin composition for coextrusion molding of the present invention comprises the above graft copolymer (X), (co) polymer (Y) containing alkyl (meth) acrylate as a main component, crosslinked fine particles and, if necessary, It can be obtained by kneading the colorant, the stabilizer, the ultraviolet absorber, the processing aid and the like to be used by a known melt kneading method. When melt-kneading,
An extruder, a Banbury mixer, a pressure kneader, a kneader such as a roll, or the like may be used.

<Laminate Molded Product> By coextruding the acrylic resin composition for coextrusion molding of the present invention and another resin,
A resin molded product having an acrylic resin on the surface layer can be obtained. The acrylic resin composition for coextrusion molding of the present invention and the resin used for coextrusion are not particularly limited.
Examples thereof include resins, ASA resins, AS resins, polystyrene resins, polycarbonate resins, vinyl chloride resins, acrylic resins, polyester resins, polyamide resins, and thermoplastic resins containing these as main components. Of these, vinyl chloride resins are preferable from the viewpoint of processability and mechanical properties. Here, the vinyl chloride-based resin is a resin obtained by homopolymerizing vinyl chloride or copolymerizing vinyl chloride mainly with other monomers. Acrylic resin composition for co-extrusion molding, as a coating material for a base material such as vinyl chloride-based resin, imparting a design property,
It can be used for the purpose of protecting the base material such as weather resistance, stain resistance and scratch resistance.

For the laminated molded article of the present invention, various resins and the acrylic resin for co-extrusion molding of the present invention are used by using a co-extrusion molding machine equipped with a plurality of extruders and a die having a molten resin merging portion. It can be obtained by cooling after coextrusion. The thickness of the acrylic resin layer in the coextrusion molded product is
Although not particularly limited, it is preferably 10 to 1000 μm, more preferably 50 to 500 μm, and further preferably 10 from the viewpoint of the hiding property of the base resin surface and the protection of the base.
It is 0 to 500 μm.

The laminated molded article obtained by coextruding the acrylic resin composition for coextrusion molding and the vinyl chloride resin of the present invention is used as a window frame profile. In addition to this, door materials,
It is also used for decorative steel sheets and the like, and in particular, molded products that use colorants in the acrylic resin layer can be used for resin sashes, window frames, etc., and can show excellent designability, impact resistance, and durability, Very high utility value.

[0057]

EXAMPLES The present invention will be specifically described below with reference to examples. Here, "parts" in Preparation Examples, Examples and Comparative Examples
Represents "parts by mass" and "%" represents "mass%" unless otherwise specified. The weight average particle diameter in the prepared latex was determined by a dynamic light scattering method using DLS-700 manufactured by Otsuka Electronics Co., Ltd.

Preparation Example 1 Graft Copolymer (X-1)
[Production of polyorganosiloxane latex (L-1)] Octamethylcyclotetrasiloxane 98 parts, γ-
2 parts of methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane-based mixture. 300 parts of distilled water in which 0.65 part of sodium dodecylbenzenesulfonate was dissolved was added to this, and the mixture was stirred with a homomixer at 9000 rpm for 2 minutes, and then passed through a homogenizer once at a pressure of 30 MPa to obtain a stable preliminary. A mixed organosiloxane latex was obtained. On the other hand, a reagent injection container,
In a reactor equipped with a cooling pipe, a jacket heater and a stirring device, 10 parts of dodecylbenzenesulfonic acid and 9 parts of distilled water were added.
0 parts was added to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. With the aqueous solution heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the completion of the addition, the temperature was maintained for 1 hour and cooled. Next, this reaction product was neutralized with a caustic soda aqueous solution to obtain a polyorganosiloxane latex (L-1). The latex thus obtained was heated at 170 ° C. for 3 days.
When the solid content was obtained by drying for 0 minutes, it was 18.0%. The weight average particle diameter of the polyorganosiloxane in the latex was 0.07 μm.

[Production of Composite Rubber (A-1) Latex]
Next, 45.2 parts of polyorganosiloxane latex (L-1), polyoxyethylene alkylphenyl ether sulfate ("Emal N" were placed in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirring device.
C-35 "(manufactured by Kao Co., Ltd.) 0.18 part was charged, and 148.5 parts of distilled water was added thereto and mixed, and then 42 parts of butyl acrylate, 0.3 part of allyl methacrylate, 1,3
-A mixture of 0.1 part of butylene glycol dimethacrylate and 0.11 part of t-butyl hydroperoxide was added. The atmosphere was replaced with nitrogen by passing a nitrogen stream through this reactor, and the temperature was raised to 60 ° C.
When the internal liquid temperature reached 60 ° C, ferrous sulfate 0.0
An aqueous solution prepared by dissolving 000075 parts, 0.02225 parts of ethylenediaminetetraacetic acid disodium salt and 0.2 parts of Rongalite in 10 parts of distilled water was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a composite rubber (A-1) latex of polyorganosiloxane and butyl acrylate rubber. A part of the latex was sampled and the weight average particle diameter of the obtained composite rubber (A-1) was measured. As a result, it was 0.13 μm.

[Production of Graft Copolymer (X-1)] After the liquid temperature of the composite rubber (A-1) latex was lowered to 70 ° C. inside the reactor, 0.25 part of Rongalit was added to 10 parts of distilled water. An aqueous solution dissolved in was added, and then a mixed solution of 2.5 parts of acrylonitrile, 7.5 parts of styrene and 0.05 parts of t-butyl hydroperoxide was added dropwise over 2 hours for polymerization. After the dropping, the temperature of 60 ° C was maintained for 1 hour, and then 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of Rongalit and "Emar NC-35" (Kao) (Manufactured by Co., Ltd.) 0.18 part was added to an aqueous solution prepared by dissolving 10 parts of distilled water, and then 10 parts of acrylonitrile, 30 parts of styrene and t-butyl hydroperoxide (0.1 part).
The mixture of 2 parts was added dropwise over 2 hours for polymerization. After the completion of the dropping, the temperature of 60 ° C. was maintained for 0.5 hours, 0.05 part of cumene hydroperoxide was added, and the temperature of 60 ° C. was maintained for 0.5 hour and then cooled. The graft copolymer latex obtained was coagulated with an aqueous solution of calcium acetate, dehydrated, and dried to obtain a graft copolymer (X-1).

Preparation Example 2 Production of Multilayer Structure Polymer (X-2) (Preparation of Example "Multilayer Structure Polymer (II)" in JP-A-5-93122) (1) Production in the first stage First, the raw material of (i) of Table 1 was put into a reaction vessel made of stainless steel having an internal volume of 50 liters, and 802.4 g of the monomer mixture of (A-1) shown in Table 2 was collectively added with stirring. Then, after nitrogen gas was blown in to make it substantially free from the influence of oxygen, the temperature was raised to 70 ° C., the raw material (ii) in Table 1 was added and polymerization was carried out for 60 minutes. Monomer mixture 1 of (A-2) shown
203.6 g was continuously added over 30 minutes for polymerization, and after the addition was completed, the polymerization was continued for another 90 minutes.

[0062]

[Table 1]

[0063]

[Table 2]

In the table, S-LN is sodium N-lauroylsarcosine and EDTA-2Na is ethylenediamine-.
4-acetic acid-2-sodium, BA is butyl acrylate, St is styrene, MMA is methyl methacrylate,
C4-DA is 1,4-butanediol diacrylate,
t-BH represents t-butyl hydroperoxide.

(2) Second-stage production: 2 kg of polymer solid content of the first-stage semi-soft crosslinked resin obtained in (1) above
In the same container containing the water, 500 g of deionized water and S-LN5
After adding a mixed aqueous solution of 0 g and 20 g of Rongalit and raising the internal temperature to 80 ° C., BA81%, St17.
5%, triallyl isocyanurate 1.1%, C4-D
A mixture obtained by adding 32 g of t-BH to 8 kg of the crosslinkable acrylic ester-based monomer mixture (B) consisting of 0.4% A,
Polymerization was continued for 150 minutes with continuous addition, and the polymerization was continued for another 180 minutes after the addition was completed. Then, a second-stage latex of an elastomer layer containing the first-stage resin inside the particles was obtained. As a result of measuring the polymer particle size of the latex at the end of the second stage by the absorbance method,
It was 0.28 μm.

(3) Production in the third stage: The same container containing 10 kg of polymer solids of the copolymer latex obtained in the above (2) and having a two-stage structure different from the first stage and the second stage. To 500g deionized water and 40g S-LN
While maintaining the internal temperature at 80 ° C while stirring
Mixture 6 consisting of 95% MA and 5% methyl acrylate
kg, 13.8 g of n-octyl mercaptan and t-
A monomer mixture (C) consisting of 9 g of BH was continuously added at a rate of 40 parts / hour. Then, the polymerization was further continued for 1 hour. Then, a multi-structured polymer (X-2) was obtained in a latex form. The polymerization rate of the monomer mixture (C) is 99.5%
That was all.

The latex was coagulated, washed and dried by the method described below to obtain a powder. 100 kg of 1.0% sulfuric acid water was charged into a stainless steel container, heated to 70 ° C. under stirring, 40 kg of the latex produced above was continuously added for 15 minutes, and then the internal temperature was raised to 90 ° C. Hold for 5 minutes. After cooling to room temperature, the polymer is filtered off and washed with deionized water to give a white creamy polymer,
This was dried at 70 ° C. for 24 hours to obtain a white powdery multilayer structure polymer (X-2).

Preparation Example 3 Production of Copolymer (Y-1):
In a reaction vessel equipped with a stirrer, methyl methacrylate 91
Part, and 100 parts of a monomer mixture of 9 parts of ethyl acrylate were added, and lauroyl peroxide was added as a polymerization initiator.
44 parts, n-octyl mercaptan 0.37 part as a chain transfer agent, and stearyl alcohol 0.1 as a release agent.
5 parts was added and dissolved by stirring. Further, 150 parts of deionized water was placed in another container, 0.5 part of polyvinyl alcohol as a dispersant and 0.5 part of sodium sulfate as a dispersion aid were added and dissolved by stirring. Then, the deionized water mixture stirred and dissolved in another container was put into a reaction container equipped with a stirrer, and stirred at 350 rpm for 15 minutes while purging with nitrogen. afterwards,
Polymerization was initiated by heating to 75 ° C, and after the polymerization peak, 95
A heat treatment was performed at 30 ° C. for 30 minutes to complete the polymerization and obtain a copolymer (Y-1). J of the obtained copolymer (Y-1)
The melt mass flow rate measured according to IS K7210 was 20 g / 10 min.

(Preparation Example 4) Production of copolymer (Y-2):
In a reaction vessel equipped with a stirrer, methylmethacrylate 90
Parts, 100 parts of a monomer mixture of 10 parts of methyl acrylate, 0.1 part of azobisisobutyronitrile as a polymerization initiator, 0.25 part of n-octyl mercaptan as a chain transfer agent, and stearyl alcohol as a release agent. 0.1
5 parts by mass was added and dissolved by stirring. Further, 150 parts by mass of deionized water was placed in another container, 0.5 parts by mass of polyvinyl alcohol as a dispersant and 0.5 parts by mass of sodium sulfate as a dispersion aid were added and dissolved by stirring. Then, the deionized water mixture stirred and dissolved in another container was put into a reaction container equipped with a stirrer, and stirred at 350 rpm for 15 minutes while purging with nitrogen. Then, the mixture was heated to 75 ° C. to start the polymerization, and after the polymerization peak, heat treatment was carried out at 95 ° C. for 30 minutes to complete the polymerization, and a copolymer (Y-2) was obtained. The melt mass flow rate of the obtained copolymer (Y-2) measured according to JIS K7210 was 10 g / 10 min.

[Examples 1-2, Comparative Examples 1-2] Graft copolymer (X-1), copolymer (Y-1), crosslinked fine particles ("MBXR-8N" manufactured by Sekisui Plastics Co., Ltd.), Colorants in Table 3
As a stabilizer, 0.4 parts of ADEKA STAB 2112 manufactured by Asahi Denka Co., Ltd., 0.1 part of ADEKA STAB LA-57, and a UV absorber of Ciba Specialty Chemicals Co., Ltd. are mixed. Made tinuvin P
0.1 parts, Mitsubishi Rayon Co., Ltd. Metabrene P530A 1 part as a processing aid, Mitsubishi Rayon Co., Ltd. Metabrene L1000 0.8 parts as a lubricant were mixed using a Henschel mixer, and this mixture was heated to 230 ° C. The mixture was supplied to a degassing extruder (PCM-30 manufactured by Ikegai Tekko Co., Ltd.) heated to 1, and kneaded to obtain pellets. As the coloring agent, 65% of zinc ferrite and the copolymer (Y-1) were used.
Using a pressure kneader, 35% of a master batch (colorant A) obtained by kneading 35% of the mixture at 200 ° C. using a pressure kneader and freeze-grinding, and 65% of titanium oxide and 35% of a copolymer (Y-1) were used. Using a masterbatch (colorant B) kneaded at 200 ° C. and freeze-pulverized, the blending amount is 100 parts by weight of the graft copolymer (X-1) and the copolymer (Y-1). It was prepared so that the zinc ferrite content was 1 part and the titanium oxide content was 2 parts.

Pellets of the acrylic resin composition for co-extrusion molding produced by the above method were dried at 80 ° C. for one day, and the obtained pellets were co-extruded with a vinyl chloride resin and molded into a window frame profile. The molding temperature of the acrylic resin composition for coextrusion molding was 210 ° C, and the molding temperature of the vinyl chloride resin was 190 ° C. The average thickness of the acrylic resin layer was 0.2 mm. At this time, coextrusion moldability, thickness stability, Charpy impact strength, low temperature impact strength, and low temperature drop weight strength of the obtained molded product were evaluated. The impact resistance was evaluated by cutting out a test piece from the window frame profile.

With respect to moldability, when coextrusion molding was continuously performed for 10 hours, ◯ was given when no plate-out occurred, Δ was given when it was slightly generated, and x was given when it was significantly generated. Regarding the thickness stability, when the difference in thickness is less than 10% of the average thickness, ◯ is 10
When it was -20%, it was evaluated as Δ, and when it exceeded 20%, it was evaluated as x.
The Charpy impact strength, the low temperature impact strength, and the low temperature drop weight strength were measured by the method according to JIS K6785. Table 3 shows the respective evaluation results.

[Example 3, Comparative Examples 3 to 4] As a colorant, 10% of calcium stearate, 10% of magnesium stearate, and 80% of zinc ferrite were mixed and pulverized to obtain a dry color (colorant a), and calcium stearate. 10%, magnesium stearate 10
% And 80% titanium oxide were mixed and finely pulverized to obtain a dry color (colorant b), and a coextrusion molded article was obtained in the same manner as in Example 1. Here, as in the case of Example 1, the amount of the coloring agent was 100 parts by weight of the total amount of the graft copolymer (X-1) and the copolymer (Y-1), and the content of zinc ferrite was 1 part by weight. The titanium content was adjusted to 2 parts. Table 3 shows the respective evaluation results.

[Example 4] A coextrusion molded article was obtained in the same manner as in Example 1 except that the copolymer (Y-2) was used. Here, the colorant A and the colorant B are blended in an amount of 1 part of zinc ferrite and titanium oxide based on 100 parts of the total amount of the graft copolymer (X-1) and the copolymer (Y-2). Was adjusted to 2 parts. The evaluation results are shown in Table 3.

[Comparative Example 5] Example method disclosed in JP-A-5-93122: Example except that the multilayer structure polymer (X-2) and Acrypet MF manufactured by Mitsubishi Rayon Co., Ltd. were used. A coextrusion molded article was obtained in the same manner as in 1. here,
The blending amounts of the colorant A and the colorant B are 100 parts by weight of the total of the multilayer structure polymer (X-2) and the acrypet MF.
Zinc ferrite content is 1 part, titanium oxide content is 2
It was prepared so as to be a part. The evaluation results are shown in Table 3.

[Comparative Example 6] Method of Example of JP-A-5-93122: A coextrusion molded article was prepared in the same manner as in Comparative Example 5 except that the colorants a and b were used as the colorants. Obtained. Here, the blending amount of the colorant is based on 100 parts in total of the multilayer structure polymer (X-2) and the acrypet MF.
Zinc ferrite content is 1 part, titanium oxide content is 2
It was prepared so as to be a part. The evaluation results are shown in Table 3.

[0077]

[Table 3]

The following can be seen from the examples and comparative examples. With the acrylic resin compositions of Examples 1 to 4, it is possible to obtain a coextrusion laminated molded article having a good molding appearance, in which plate-out is unlikely to occur, and in particular, Examples 1 to 2
The laminated molded product of Example 4 is excellent in productivity and design because plate-out does not occur even after continuous production for a long time. Laminated articles using the acrylic resin compositions of Examples 1 to 4 exhibit the impact resistance described in JIS K6785, which is necessary for window frame profiles, and have high industrial utility value as building material members. The acrylic resin compositions of Comparative Example 1 and Comparative Example 3 have good impact resistance of a laminated molded product using the same, but plate-out easily occurs during coextrusion molding, and the designability of the coextrusion molded product is high. It has low industrial utility value because it damages The acrylic resin compositions of Comparative Example 2 and Comparative Examples 4 to 6 do not cause plate-out when coextruding the acrylic resin compositions and have good designability, but all of them are JIS K6785.
Since the impact resistance described is not satisfied and the material cannot be used as a constituent material of the opening, there is a limitation in the usable application, so that the industrial utility value is low.

[0079]

As described above, the acrylic resin composition for coextrusion molding of the present invention contains the above-mentioned specific graft copolymer (X) and an alkyl (meth) acrylate as main components (co). Average particle diameter containing alkyl (meth) acrylate as a main component based on 100 parts by mass of the thermoplastic resin composition comprising the polymer (Y), the graft copolymer (X) and the (co) polymer (Y). Since it contains 1 to 20 parts by mass of crosslinked fine particles of 1 to 20 μm,
It is possible to obtain a coextrusion molded article having good impact resistance in a low-temperature atmosphere that satisfies the performance of an impact test according to SK6785, and good weatherability and moldability.

A (co) polymer (Y) containing an alkyl (meth) acrylate as a main component is JIS K7210.
Melt mass flow rate (MFR) measured according to
If the value is in the range of 15 to 25 g / 10 min, a coextrusion molded article having an acrylic resin layer having a uniform thickness and further improved impact resistance can be obtained. In addition, plateout of the colorant can be further suppressed as long as it is colored using a colorant masterbatch using an acrylic resin as a binder.

The laminated molded article of the present invention is obtained by co-extruding and molding the acrylic resin composition for co-extrusion molding of the present invention and a vinyl chloride resin.
It has good impact resistance in a low temperature atmosphere that satisfies the performance of an impact test according to 785, and good weatherability and moldability. Such a laminated molded article is used as a window frame profile, and has excellent designability, impact resistance, and
It can exhibit durability and has extremely high industrial utility value.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F070 AA18 AA32 AA34 AA59 AC83                       AE04 FA01 FB03 FC05                 4F100 AK15B AK25A AK27A AK52A                       AL01A AL04A AL05A AN00A                       CA13A CA30A DE01A EH202                       EJ05A GB08 HB00A JA06A                       JK10 JL01 JL09 JL10A                       YY00A                 4J002 BG03X BG033 BN21W DB006                       DE116 DE136 FD096 GL00

Claims (5)

[Claims] 1. A composite rubber (A) comprising a polyorganosiloxane (a-1) and a polyalkyl acrylate (a-2), and at least an aromatic alkenyl, a vinyl cyanide compound and an alkyl (meth) acrylate. A graft copolymer (X) obtained by graft-polymerizing one or more kinds of monomers or monomer mixtures (B), and a (co) polymer (Y) containing an alkyl (meth) acrylate as a main component. 1 to 100 parts by mass of the thermoplastic resin composition composed of the graft copolymer (X) and the (co) polymer (Y), the average particle diameter of which is mainly composed of alkyl (meth) acrylate 1 to
An acrylic resin composition for coextrusion molding, which comprises 1 to 20 parts by mass of 20 μm crosslinked fine particles. 2. The (co) polymer (Y) containing an alkyl (meth) acrylate as a main component has a melt mass flow rate (MFR) value measured according to JIS K7210 in the range of 15 to 25 g / 10 min. The acrylic resin composition for coextrusion molding according to claim 1, which is a resin. 3. The acrylic resin composition for coextrusion molding according to claim 1 or 2, which is colored by using a colorant masterbatch containing an acrylic resin as a binder. 4. A laminated molded article obtained by co-extruding and molding the acrylic resin composition for co-extrusion molding according to claim 1 and a vinyl chloride resin. 5. A window frame profile, comprising the laminated molded product according to claim 4.