JP2000007745A - Flexible thermoplastic molding and industrial member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flexible thermoplastic molding having a flexibility, weather resistance, processibility and designability suitable for use wherein flexible polyvinyl chloride may be used, and an industrial part. SOLUTION: A flexible thermoplastic molding is obtained by heat molding a graft copolymer prepared by graft polymerizing a composite rubber ((A)+(B)) comprising (A) a polyorganosiloxane and (B) an alkyl (meth)acrylate rubber with (C) one or more monomers chosen from aromatic alkenyl compounds, acrylic esters, methacrylic esters and vinyl cyanide compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to light fastness, softness,
The present invention relates to a soft thermoplastic resin molded article excellent in workability and design and an industrial part using the same.

[0002]

2. Description of the Related Art Vinyl chloride resin has excellent processability,
Utilizing mechanical strength, texture, oil resistance, and the like, it is used in various fields such as automobile parts, electric parts, and building material parts.

[0003] In particular, soft polyvinyl chloride obtained by blending a plasticizer with polyvinyl chloride is processed into various parts by various types of thermoforming such as extrusion molding, calendering molding, injection molding, etc., and is used for agricultural films / sheets and automobiles. Interior skin materials, interior skin materials, packaging films, floor sheets, wall materials,
Wire and cable covering materials, tapes, automobile exterior mall parts, various packing materials and miscellaneous goods such as toys, dolls, plugs and household appliances parts such as vacuum cleaners, refrigerators, washing machines, cord plugs, door knobs, shoe soles and bamboo fences It is used for various industrial parts such as building materials such as artificial wood and cushioning materials.

[0004] However, these polyvinyl chlorides
It is poorly recyclable as a raw material, and harmful substances such as hydrogen chloride and dioxin are generated during incineration when it is not needed.The effects of these incinerated substances on the human body and the global environment have become problems. There is a strong demand for the development of an industrial member that can be replaced with a member made of soft polyvinyl chloride in use.

[0005] In place of these industrial parts in which soft polyvinyl chloride is used, various elastomers such as olefin-based elastomers, styrene-based elastomers, polyester-based elastomers, polyamide-based elastomers, polyurethane-based elastomers, and natural rubber And ethylene-propylene rubber, isoprene rubber, silicone rubber, butadiene rubber, NBR, SBR
Various synthetic rubbers, such as soft acrylonitrile-butadiene-styrene copolymer (soft ABS resin) and soft acrylonitrile-acryl rubber-styrene copolymer (soft ASA resin) have been industrially studied.

Of these, olefin elastomers, soft ABS resins and soft ASA resins are used in automobile exterior malls, automobile interior skin materials and building material parts from the viewpoints of production cost, recyclability, ease of molding and durability. It has been industrially studied as a substitute for flexible polyvinyl chloride.

However, olefin-based elastomers have poor weldability with other resins, for example, cannot be co-extruded with a hard ABS resin, which limits the molding method and the intended use, and also impairs weather resistance and surface damage. Because the stickiness is also poor,
It cannot be said to be sufficient as a substitute material for flexible polyvinyl chloride.

On the other hand, a soft ABS resin has many chemically unstable double bonds in polybutadiene which is a rubber component, and thus is easily deteriorated by ultraviolet rays or the like. Such a surface treatment is required, and the cost required for such a surface treatment is not sufficient.

Further, the soft ASA resin has sufficient performance in terms of weather resistance and solvent resistance, but has a relatively high glass transition temperature of a rubber component, and thus has poor flexibility at low temperatures, especially at low temperatures. Because the use of automotive parts or building material parts that require softness is limited,
Low industrial value.

Conventionally, as a method for improving the weather resistance of ABS resin and the low-temperature characteristics of ASA resin, JP-A-4-100
No. 812 proposes to use a graft copolymer in which a vinyl monomer is graft-polymerized to a composite rubber having a structure in which polyorganosiloxane and alkyl (meth) acrylate rubber are entangled with each other so that they cannot be separated. I have.

[0011]

However, the composite rubber-based graft copolymer described in Japanese Patent Application Laid-Open No. 4-100812 is added to other hard resins to improve the impact resistance.
It is an impact resistance improving material for improving mechanical strength, and there is no description in the specification of using a graft copolymer as a structural material for a soft material, and there is no suggestion for such a utilization technique. I haven't.

In the examples of JP-A-4-100812, a composite rubber-based graft copolymer is extruded and shaped, and then a test piece is prepared by injection molding. Although described in terms of measurement, these are intended to specify the characteristics of the composite rubber-based graft copolymer as an impact modifier, that is, the lower the tensile modulus, the more effective the impact modifier. It is suggested that the higher the gloss, the higher the gloss, the better the molded appearance after adding to the resin, and the use of the composite rubber-based graft copolymer as a soft thermoplastic resin molded article and the soft poly No mention is made of its use as an industrial component in applications where vinyl chloride can be used.

An object of the present invention is to obtain a soft thermoplastic resin molded article and industrial parts having softness, weather resistance, workability, and design properties suitable for applications in which soft polyvinyl chloride can be used.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies on the softness, molded appearance, and weather resistance of a resin molded product obtained by thermoforming a graft copolymer. Organosiloxane and alkyl (meth)
A molded article obtained by thermoforming a graft copolymer containing a composite rubber composed of an acrylate rubber shows unprecedented excellent softness, molding appearance, weather resistance and moldability, and shows that conventional soft polyvinyl chloride Of the present invention have been found to exhibit the required performance as industrial parts used in applications where they can be used.

That is, the gist of the present invention is as follows.
(A) polyorganosiloxane and (B) alkyl (meth)
Composite rubber composed of acrylate rubber ((A) + (B))
By thermoforming a graft copolymer obtained by graft polymerization of one or more monomers selected from (C) an aromatic alkenyl compound, an acrylate, a methacrylate and a vinyl cyanide compound; The present invention relates to the obtained soft thermoplastic resin molded article and its industrial parts.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The polyorganosiloxane (A) constituting the graft copolymer according to the present invention is not particularly limited, but is preferably a polyorganosiloxane containing a vinyl polymerizable functional group. . More preferably, it is a polyorganosiloxane containing a vinyl polymerizable functional group and further having a crosslinked structure via a siloxane bond.

As a method for producing the polyorganosiloxane, a latex obtained by emulsifying a mixture of a diorganosiloxane and a siloxane having a vinyl polymerizable functional group or, if necessary, a mixture containing a siloxane-based crosslinking agent with an emulsifier and water is used. After homogenization using a homomixer that atomizes by shearing force due to high-speed rotation or a homogenizer that atomizes by jet power from a high-pressure generator, polymerize at high temperature using an acid catalyst, and then use an alkaline substance. It neutralizes acids. As a method for adding the acid catalyst used for the 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 finely divided into a high-temperature acid aqueous solution at a constant rate.

The size of the polyorganosiloxane particles is not particularly limited.
In consideration of the softness of the molded article and the appearance of the molded article, the weight average particle diameter is preferably from 0.02 μm to 0.5 μm,
More preferably, it is 0.05 μm to 0.3 μm.

The diorganosiloxane used in the production of the polyorganosiloxane includes a diorganosiloxane-based cyclic compound having three or more ring members, a low-polymerization degree linear polysiloxane, and the like. Is preferred. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These may be used alone or as a mixture of two or more.

The siloxane containing a vinyl polymerizable functional group is a siloxane containing a vinyl polymerizable functional group and capable of bonding to a diorganosiloxane via a siloxane bond. Considering the reactivity with the diorganosiloxane, Various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane,
methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane, and γ-mercaptopropyldimethoxy Mercaptosiloxanes such as methylsilane and γ-mercaptopropyltrimethoxysilane are exemplified.

These vinyl polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more.

As the siloxane-based crosslinking agent, a trifunctional or tetrafunctional silane crosslinking agent, for example, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane and the like are used.

As the emulsifier used in the production of the polyorganosiloxane according to the present invention, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like. Is used.
Particularly, sulfonic acid emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable. These emulsifiers are used in an amount of about 0.05 to 5 parts by weight based on 100 parts by weight of the siloxane mixture. If the amount used is small, the dispersion state becomes unstable and the emulsified state with a fine particle diameter cannot be maintained. On the other hand, if the amount is too large, the resin molded article caused by the emulsifier becomes extremely colored, which is inconvenient.

The method of mixing the siloxane mixture, emulsifier, water and / or acid catalyst includes mixing by high-speed stirring and mixing by a high-pressure emulsifying device such as a homogenizer. The method using a homogenizer is a method of mixing a polyorganosiloxane latex. This is a preferable method because the particle size distribution is reduced.

Examples of the acid catalyst used for the polymerization of the polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acids, aliphatic substituted benzenesulfonic acids and aliphatic substituted naphthalenesulfonic acids, and mineral acids such as sulfuric acid, hydrochloric acid and nitric acid. . These acid catalysts are used alone or in combination of two or more. Among these, aliphatic substituted benzenesulfonic acid is preferable because of excellent stabilizing action of the polyorganosiloxane latex, and n-dodecylbenzenesulfonic acid is particularly preferable. Also, n-
When 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 of the polyorganosiloxane is 5
The temperature is preferably 0 ° C or more, more preferably 80 ° C or more.

The polymerization time of the polyorganosiloxane is 2 hours or more, more preferably 5 hours or more when the acid catalyst is mixed with a siloxane mixture, an emulsifier and water to form fine particles, and more preferably 5 hours or more. In the method of lowering the latex in which the siloxane mixture has been made finer, it is preferable to hold the latex for about 1 hour after the completion of dropping of the latex.

The termination of the polymerization can be carried out by cooling the reaction solution and neutralizing the latex with an alkaline substance such as caustic soda, caustic potash and sodium carbonate.

The alkyl (meth) acrylate rubber (B) constituting the graft copolymer according to the present invention is a polymer of an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate, and is a composite rubber (( A) + (B)) is obtained by impregnating the polyorganosiloxane latex prepared by the above method with an alkyl (meth) acrylate component composed of an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate, followed by polymerization. Can be manufactured.

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, 2-
Examples thereof include alkyl acrylates such as ethylhexyl acrylate and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate, and use of n-butyl acrylate is particularly preferable.

Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate. , Triallyl isocyanurate and the like. The amount of the polyfunctional alkyl (meth) acrylate used is 0.1 to 20% by weight, preferably 0.2 to 5% by weight in the alkyl (meth) acrylate component.

(A) in the graft copolymer according to the present invention
A composite rubber ((A) + (B)) comprising a polyorganosiloxane and (B) an alkyl (meth) acrylate rubber is prepared by adding the above alkyl (meth) acrylate component to a polyorganosiloxane latex and subjecting it to a usual radical polymerization. It can be produced by polymerizing with the action of an initiator. As a method of adding an alkyl (meth) acrylate,
There are two methods: (A) a method of mixing with a polyorganosiloxane latex at a time, and (A) a method of dropping into a polyorganosiloxane latex at a constant speed. In consideration of the processability and molding appearance of the obtained resin molded article containing the graft copolymer, a method of simultaneously mixing with the latex of (A) the polyorganosiloxane component is preferable.

As the radical polymerization initiator used in the polymerization, a peroxide, an azo initiator or a redox initiator obtained by combining an oxidizing agent and a reducing agent is used. Among these, a redox initiator is preferable, and a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide is particularly preferable.

In the radical polymerization, an emulsifier can be added if necessary. As the emulsifier, nonionic, anionic and cationic emulsifiers are used.

The ratio of the component (A) to the component (B) in the composite rubber ((A) + (B)) constituting the graft copolymer according to the present invention is not particularly limited. Considering the ease of molding and the appearance of the molded product obtained by thermoforming the graft copolymer, preferably, the component (A) is 1 to 99 parts by weight, and the component (B) is 100 parts by weight of the composite rubber. In a range of 99 to 1 part by weight, more preferably 10 to 90 parts by weight of (A) and 90 to 90 parts by weight of component (B).
The content is in the range of 10 to 10 parts by weight.

The graft copolymer according to the present invention is obtained by adding at least one kind of alkenyl aromatic compound, methacrylic acid ester, acrylic acid ester and vinyl cyanide compound to the composite rubber produced by emulsion polymerization as described above. It can be produced by graft polymerization of a monomer.

Among the monomer units constituting the graft polymerization component (C), aromatic alkenyl compounds include, for example, styrene, α-methylstyrene and vinyl toluene, and methacrylic acid esters include, for example, methyl methacrylate and ethyl methacrylate. , 2-ethylhexyl methacrylate, and the like. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, and the like.

In the graft polymerization, a composite rubber ((A) + (B)) is used.
And at least one monomer selected from aromatic alkenyl compounds, methacrylic esters, acrylic esters and vinyl cyanide compounds, and the polymerization can be carried out in one stage or in multiple stages by a radical polymerization technique.

Further, various chain transfer agents for adjusting the molecular weight and the graft ratio of the graft polymer can be added to the monomers used in the graft polymerization.

The contents of the components (A), (B) and (C) constituting the graft copolymer of the present invention are as follows:
Although not particularly limited, preferably, the durometer A hardness of the molded article obtained by thermoforming the graft copolymer measured by a method in accordance with JIS K7215 is 30 to
It is the content of each component showing the range of 80.

J of the molded article obtained by thermoforming the graft copolymer
When the durometer A hardness measured by a method in accordance with IS K7215 is less than 30, the shape retention of the molded article tends to decrease due to insufficient rigidity, and when it exceeds 80, the softness is insufficient. This tends to limit the use as an industrial part in applications where flexible polyvinyl chloride can be used.

In consideration of both the shape retention and the softness of the molded product, the durometer A hardness of a more preferable molded product measured by a method in accordance with JIS K7215 is 45 to 75.
JIS K7215 for molded articles
Durometer A hardness measured by a method according to
It is in the range of ~ 70.

JIS K721 of the above preferred molded article
Components (A) and (B) constituting the graft copolymer exhibiting a durometer A hardness measured by a method according to No. 5.
The preferred content of component (C) is as follows: component (A) and component (B) based on 100 parts by weight of the graft copolymer.
Is in the range of 50 to 99 parts by weight, and the component (C) is in the range of 50 to 1 part by weight. More preferably, the total of the components (A) and (B) is 70 to 99 parts by weight, and the component (C) is in the range of 70 to 99 parts by weight. 30 ~
1 part by weight, more preferably 85 to 95 parts by weight of the total of the component (A) and the component (B), and 1 part by weight of the component (C).
It is in the range of 5 to 5 parts by weight.

Since the component (C) is a hard component, when the content in the graft copolymer increases, the softness of the molded article of the present invention obtained by thermoforming tends to decrease. When the content of C) decreases, the molding processability and molding appearance of the molded article tend to decrease.

The average particle size of the graft copolymer prepared as described above is not particularly limited.
Considering the processability and appearance of the molded article of the present invention obtained by thermoforming the graft copolymer, the thickness is preferably 0.05 to 0.5 μm, more preferably 0.10 to 0.5 μm.
30 μm.

The graft copolymer according to the present invention can be recovered by putting the graft copolymer latex produced as described above into hot water in which a coagulant is dissolved, and coagulating and solidifying. As the coagulant, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and metal salts such as calcium chloride, calcium acetate and aluminum sulfate can be used.

The flexible thermoplastic resin molded article of the present invention is produced by thermoforming the graft copolymer produced by the above method.

Examples of the thermoforming method include injection molding, extrusion molding, calender molding, press molding, transfer molding, hollow molding, flash molding and cast molding. Among them, applications in which soft polyvinyl chloride can be used. In consideration of use as an industrial component in the above, it is preferable to manufacture the product by extrusion molding.

The soft thermoplastic resin molded article of the present invention can be produced by co-extrusion molding with a hard thermoplastic resin.

The hard thermoplastic resin used at this time includes:
Polyolefin resin, polyamide resin, ABS resin, A
SA resins, acrylic resins, polycarbonate resins, blends of polycarbonate resins with ABS or ASA resins, polyester resins and blends thereof with ABS resins, polystyrene resins, modified PPE resins, and the like. ABS resin, ASA resin, acrylic resin, and polycarbonate resin are preferable in consideration of the adhesiveness with the copolymer molded article.

The soft thermoplastic resin molded article obtained by thermoforming the graft copolymer according to the present invention includes:
Processing aids, stabilizers, release agents for improving thermoformability, lightfastness improvers for improving durability, antistatic agents, and coloring agents such as pigments and dyes can be included.

Among these, molding burn during thermoforming,
As processing aids for improving retention deterioration and molding appearance,
Acrylic polymer-based processing aids are preferred and are commercially available as Metablen L1000.

The soft thermoplastic resin molded article of the present invention is used as various industrial parts in which soft polyvinyl chloride can be used, such as automobile exterior molding parts, automobile interior skin materials and building material parts.

Among these, as exterior car molding parts,
Front wind mall, quarter wind mall,
Wind malls such as back wind malls, bumper moldings, wheel arch moldings, door belt moldings, side moldings, step moldings, roof moldings, food top moldings, luggage moldings, etc., which are manufactured from flexible polyvinyl chloride Same formability as in the case,
Molded appearance, adhesion to hard resin, flexibility, paintability and scratch resistance are required.

Examples of the vehicle interior skin material include an instrument panel, a front pillar trim, a door trim, a shift lever, various consoles, and a skin material for a head lining. These are made of soft polyvinyl chloride. Same moldability as
Molded appearance, adhesion to hard resin, flexibility, paintability and scratch resistance are required.

The building material parts include various interior skin materials, cushion materials, artificial wood, window frame members, window frame seal materials, door skin materials, stair non-slip materials, handrail materials, plastic tiles, rain gutters, and the like. Wallpaper materials, wall materials, etc., which require the same moldability, mold appearance, adhesion to hard resin, flexibility, paintability and scratch resistance as those made of soft polyvinyl chloride Become.

[0057]

EXAMPLES The present invention will be described below with reference to examples. In addition,
In Reference Examples, Examples and Comparative Examples, "parts" and "%" are "parts by weight" and "% by weight" unless otherwise specified.
Means

The average particle size of the polymer in the latex in the reference example was determined by a dynamic light scattering method using DLS-700 manufactured by Otsuka Electronics Co., Ltd.

The durometer A hardness in the examples and comparative examples was measured according to JIS K7215 test method.

The sheet formability of the resin compositions in Examples and Comparative Examples was evaluated in three stages by visually examining the releasability of the molded product from the transfer roll in the molding process from the transfer roll during extrusion to the winding device. I went. The criteria for the determination are as follows. A: Good releasability,
B: Slightly poor releasability, C: Poor releasability The appearance of the resin compositions in Examples and Comparative Examples is as follows:
The degree of gloss unevenness and the degree of planar smoothness of the surface of the sheet-like molded product produced by extrusion molding were visually evaluated in four stages. The criteria for the determination are as follows.
A: no gloss unevenness / good surface smoothness, B: glossy unevenness / good surface smoothness, C: no gloss unevenness / bad surface smoothness, D:
With uneven gloss and poor surface smoothness (Reference Example 1) Polyorganosiloxane latex (S
Preparation of -1) 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. 100 parts of the above mixed siloxane was added to 200 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were dissolved, and 10,000 was mixed with a homomixer.
After pre-stirring at 300 rpm,
The mixture was emulsified and dispersed at a pressure of kg / cm ² to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours while mixing and stirring, and allowed to stand at 20 ° C.
After 8 hours, the pH of this latex was neutralized to 7.4 with an aqueous sodium hydroxide solution to complete the polymerization, thereby obtaining a polyorganosiloxane latex. The polymerization rate of the obtained polyorganosiloxane was 89.5%, and the average particle size of the polyorganosiloxane was 0.16 μm.

Example 1 Production of Soft Thermoplastic Resin Molded Product (N-1) The polyorganopolymer prepared in Reference Example 1 was placed in a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirring device. 33 parts of siloxane latex were collected, 1.4 parts of polyoxyethylene alkyl phenyl ether sulfate (Emal NC-35 manufactured by Kao Corporation), and distilled water 27
One part was added, the atmosphere was replaced with nitrogen, the temperature was raised to 50 ° C, and n-
A mixed liquid of 78.4 parts of butyl acrylate, 1.6 parts of allyl methacrylate and 0.40 part of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and the mixed liquid was permeated into the polyorganosiloxane particles. Then, a mixture of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged to start radical polymerization. After holding for a while, the polymerization was completed to obtain a composite rubber latex. A part of this latex was collected and the average particle size of the composite rubber was measured.
m.

A mixture of 0.05 part of tert-butyl hydroperoxide and 10 parts of methyl methacrylate was added dropwise to the composite rubber latex at 70 ° C. for 15 minutes, and then kept at 70 ° C. for 4 hours to form a composite rubber latex. The graft polymerization of was completed. The polymerization rate of methyl methacrylate was 96.4%. The measured average particle diameter of the obtained graft copolymer was 0.24 μm. Next, the obtained graft copolymer latex was dropped into 400 parts of hot water containing 1.5% of calcium chloride, and coagulated.
After separating, washing and drying at 75 ° C. for 16 hours, a powdery composite rubber-based graft copolymer was obtained.

Graft copolymer 1 prepared as described above
00 parts and acrylic polymer processing aid Metablen L100
2 (Mitsubishi Rayon Co., Ltd.) was mixed using a Henschel mixer.

Next, the mixture was mixed with 70 mm in width and 2 mm in height.
Using a single-screw extruder (manufactured by Thermoplastics Co., Ltd.) with a screw diameter of 25 mm and a transfer roll and a winding device equipped with a T die of 200 mm in barrel temperature.
Extrusion molding was performed at a temperature of 80 ° C., a roll temperature of 80 ° C., and a screw rotation speed of 50 rotations / minute to obtain a soft resin molded product (N-1) having a width of 70 mm and a thickness of 1 mm.

Table 1 shows the molding processability, molding appearance, and durometer A hardness measurement results of the molded product N-1.

Example 2 Production of Soft Thermoplastic Resin Molded Product (N-2) The polyorgano resin prepared in Reference Example 1 was placed in a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirring device. 266 parts of siloxane latex were collected and distilled water 10
9 parts were added, the atmosphere was replaced with nitrogen, and the temperature was raised to 50 ° C. to give n-
A mixture of 9.8 parts of butyl acrylate, 0.2 part of allyl methacrylate and 0.05 part of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and the mixture was permeated into the polyorganosiloxane particles. Then, a mixture of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged to start radical polymerization. After holding for a while, the polymerization was completed to obtain a composite rubber latex. A part of this latex was collected and the average particle size of the composite rubber was measured.
m.

A mixture of 0.05 part of tert-butyl hydroperoxide and 10 parts of methyl methacrylate was added dropwise to the composite rubber latex at 70 ° C. for 15 minutes, and then maintained at 70 ° C. for 4 hours to form a composite rubber latex. The graft polymerization of was completed. The polymerization rate of methyl methacrylate was 96.8%. The measured average particle size of the obtained graft copolymer was 0.18 μm. Next, the obtained graft copolymer latex was dropped into 400 parts of hot water containing 1.5% of calcium chloride, and coagulated.
After separating, washing and drying at 75 ° C. for 16 hours, a powdery composite rubber-based graft copolymer was obtained.

Graft copolymer 1 prepared as described above
00 parts and acrylic polymer processing aid Metablen L100
2 (Mitsubishi Rayon Co., Ltd.) was mixed using a Henschel mixer.

Next, the mixture was mixed with 70 mm in width and 2 mm in height.
Using a single-screw extruder (manufactured by Thermoplastics Co., Ltd.) with a screw diameter of 25 mm and a transfer roll and a winding device equipped with a T die of 200 mm in barrel temperature,
Extrusion molding was performed at a roll temperature of 80 ° C. and a screw rotation speed of 50 rotations / minute to obtain a soft resin molded product (N-2) having a width of 70 mm and a thickness of 1 mm.

Table 1 shows the molding processability, molding appearance, and durometer A hardness measurement results of the molded product N-2.

Example 3 Production of Soft Thermoplastic Resin Molded Product (N-3) A polyorganopolymer prepared in Reference Example 1 was placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device. 100 parts of siloxane latex were collected, 1.4 parts of polyoxyethylene alkyl phenyl ether sulfate (Emal NC-35 manufactured by Kao Corporation), and distilled water 22
After adding 5 parts and purging with nitrogen, the temperature was raised to 50 ° C., and n-
A mixed liquid of 39.2 parts of butyl acrylate, 0.8 part of allyl methacrylate and 0.20 part of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and the mixed liquid was permeated into the polyorganosiloxane particles. Then, a mixture of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged to start radical polymerization. After holding for a while, the polymerization was completed to obtain a composite rubber latex. A part of this latex was collected, and the average particle size of the composite rubber was measured.
m.

A mixture of 0.14 part of tert-butyl hydroperoxide, 9 parts of acrylonitrile and 21 parts of styrene was added to this composite rubber latex at 70 ° C. for 45 minutes.
Then, the mixture was kept at 70 ° C. for 4 hours to complete the graft polymerization onto the composite rubber. The total polymerization rate of acrylonitrile and styrene was 98.4%. The measured average particle diameter of the obtained graft copolymer was 0.24 μm. Next, the obtained graft copolymer latex was dropped into 400 parts of hot water containing 1.5% by weight of calcium chloride, coagulated, separated and washed, and then 75 ° C.
For 16 hours to obtain a powdery composite rubber-based graft copolymer.

Graft copolymer 1 prepared as described above
00 parts and acrylic polymer processing aid Metablen L100
2 (Mitsubishi Rayon Co., Ltd.) was mixed using a Henschel mixer.

Next, the mixture was mixed with 70 mm in width and 2 mm in height.
Using a single-screw extruder (manufactured by Thermoplastics Co., Ltd.) with a screw diameter of 25 mm and a transfer roll and a winding device equipped with a T die of 200 mm in barrel temperature,
Extrusion molding was performed at a roll temperature of 80 ° C. and a screw rotation speed of 50 rotations / minute to obtain a soft resin molded product (N-3) having a width of 70 mm and a thickness of 1 mm.

Table 1 shows the molding processability, molding appearance, and durometer A hardness measurement results of the molded product N-3.

Example 4 Production of Soft Thermoplastic Resin Molded Product (N-4) The polyorgano resin prepared in Reference Example 1 was placed in a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirring device. 33 parts of siloxane latex were collected, 1.4 parts of polyoxyethylene alkyl phenyl ether sulfate (Emal NC-35 manufactured by Kao Corporation), and distilled water 27
One part was added, the atmosphere was replaced with nitrogen, the temperature was raised to 50 ° C, and n-
A mixed liquid of 39.2 parts of butyl acrylate, 0.8 part of allyl methacrylate and 0.20 part of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and the mixed liquid was permeated into the polyorganosiloxane particles. Then, a mixture of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged to start radical polymerization. After holding for a while, the polymerization was completed to obtain a composite rubber latex. A part of this latex was collected, and the average particle size of the composite rubber was measured.
m.

A mixture of 0.23 part of tert-butyl hydroperoxide, 15 parts of acrylonitrile and 35 parts of styrene was added to the composite rubber latex at 70 ° C. for 7 hours.
Dropwise over 5 minutes, then hold at 70 ° C. for 4 hours,
Graft polymerization to the composite rubber was completed. The total polymerization rate of acrylonitrile and styrene was 98.7%.
The measured average particle diameter of the obtained graft copolymer was 0.24 μm. Next, the obtained graft copolymer latex was dropped into 400 parts of hot water containing 1.5% by weight of calcium chloride, coagulated, separated, washed, and then washed.
Drying at 16 ° C. for 16 hours gave a powdery composite rubber-based graft copolymer.

Graft copolymer 1 prepared as described above
00 parts and acrylic polymer processing aid Metablen L100
2 (Mitsubishi Rayon Co., Ltd.) was mixed using a Henschel mixer.

Next, the mixture was mixed with 70 mm in width and 2 mm in height.
A single screw extruder with a screw diameter of 25 mm equipped with a T die (manufactured by Thermoplastics Co., Ltd. and using an extruder consisting of a transfer roll and a winding device, a barrel temperature of 200 ° C., a roll temperature of 80 ° C., and a screw rotation speed of 50 rpm) Under the conditions described above, to obtain a soft resin molded product (N-4) having a width of 70 mm and a thickness of 1 mm.

Table 1 shows the molding processability, molding appearance, and durometer A hardness measurement results of the molded product N-4.

Comparative Example 1 Production of Soft Thermoplastic Resin Molded Product (H-1) Polyoxyethylene alkyl phenyl ether sulfate (Hydrogen) was placed in a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirring device. 3.4 parts of Kao Corporation (Emal NC-35) and 295 parts of distilled water were added, the atmosphere was replaced with nitrogen, the temperature was raised to 50 ° C, 88.2 parts of n-butyl acrylate, 1.8 parts of allyl methacrylate. Department and te
A mixture of 0.40 parts of rt-butyl hydroperoxide was charged and stirred for 30 minutes, and then ferrous sulfate (0.002 parts) was added.
Parts, disodium ethylenediaminetetraacetate 0.006
, A mixed solution of 0.26 parts of Rongalite and 5 parts of distilled water were charged to start radical polymerization, and then kept at an internal temperature of 70 ° C. for 2 hours to complete the polymerization to obtain an acrylic rubber latex. A part of this latex was collected and the average particle diameter of the rubber was measured to be 0.16 μm.

The acrylic rubber latex was added with tert
A mixture of 0.05 parts of -butyl hydroperoxide and 10 parts of methyl methacrylate was added dropwise at 70 ° C. over 15 minutes, and then maintained at 70 ° C. for 4 hours to complete the graft polymerization onto the acrylic rubber. The polymerization rate of methyl methacrylate was 95.7%. When the average particle diameter of the obtained graft copolymer was measured, it was 0.19 μm.
Met. Next, the obtained graft copolymer latex was dropped into 400 parts of hot water containing 1.5% by weight of calcium chloride, coagulated, separated, washed, and dried at 75 ° C. for 16 hours.
A powdery acrylic rubber-based graft copolymer was obtained.

Graft copolymer 1 prepared as described above
00 parts and acrylic polymer processing aid Metablen L100
2 (Mitsubishi Rayon Co., Ltd.) was mixed using a Henschel mixer.

Next, this mixture was prepared to be 70 mm wide and 2 mm high.
Using a single-screw extruder (manufactured by Thermoplastics Co., Ltd.) with a screw diameter of 25 mm and a transfer roll and a winding device equipped with a T die of 200 mm in barrel temperature,
Extrusion molding was performed under the conditions of a roll temperature of 80 ° C. and a screw rotation speed of 50 rotations / minute to obtain a soft resin molded product (H-1) having a width of 70 mm and a thickness of 1 mm.

Table 1 shows the molding processability, molding appearance, and durometer A hardness measurement results of the molded product H-1.

Example 5 Production of a Two-Layer Extruded Product A two-layer sheet extruder combining two single-screw extruders having a screw diameter of 25 mm, an extruder comprising a transfer roll and a winding device, and a barrel temperature of 200 were used. C. and a roll temperature of 80.degree. C., and a graft copolymer / acrylic polymer processing aid mixture prepared in Example 1 and an ABS resin (Diapet ABS SW- manufactured by Mitsubishi Rayon Co., Ltd.).
3 was performed to form a two-layer sheet having a width of 70 mm, a graft copolymer layer of 1 mm, and an ABS layer of 2 mm.

The adhesion between the two layers of the two-layer extruded product was good.

[0088]

[Table 1]

The following was made clear from the examples and comparative examples.

1) The soft thermoplastic resin molded article of the embodiment is
Both have good sheet moldability and sheet mold appearance. 2) The soft thermoplastic resin molded article of the comparative example containing no polyorganosiloxane in the graft copolymer is accompanied by poor roll releasability during molding and is obtained. Molded articles having poor surface smoothness and thus poor sheet formability and molded appearance have low industrial utility value.

3) The resin molded products of Examples 1 to 4 exhibit a relatively low durometer A hardness, and the resin molded products excellent in softness are used for applications in which flexible polyvinyl chloride can be used. The industrial value is high. In particular, the durometer A hardness of the soft thermoplastic resin molded articles of Examples 1 and 2 shows a particularly low value, and the soft thermoplastic resin molded article having such a low durometer A hardness is used for automobile exterior molding parts and automobile interior skin. Since it can be used for applications requiring a high level of softness, such as materials and building material parts, it has high industrial utility value.

4) From Example 5, the composite rubber-based graft copolymer and the ABS resin were co-extruded to obtain
A resin molded article having excellent interfacial adhesion can be obtained.

[0093]

As described above, the present invention has the following remarkable effects, and its industrial value is extremely large. 1) The soft thermoplastic resin molded article according to the present invention has light resistance,
Excellent in softness, moldability and mold appearance. 2) In particular, the balance between softness, molding appearance and molding workability is good, and it can be used for applications where conventional soft polyvinyl chloride can be used, and various industrial materials, especially automobile exterior molding parts, automobile interior skin materials and Its value as a building material component is extremely high.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 51/04 C08L 51/04 F term (reference) 3D023 BA01 BB01 BC00 BD00 BE04 BE06 BE31 4F070 AA08 AA12 AA32 AA34 AA47 AA50 AA52 AA54 AA60 AB08 AB11 AB21 FA03 FC05 4F208 AA21 AA45G AH23 AH26 AH48 AR20 MA05 MA10 MB01 MB22 MC03 MG04 MG11 MG22 4J002 BB01W BC03W BG03W BN12W BN12X BN15W BN21X BN22X CF05W CG00A FD00 FD00A FD01A AC18 AC22 AC31 AC32 BA05 BA06 BA27 BA31 BB01 BB02 CA07 DA04 DA07 DA09 DA10 DA11 DA12 DA13 DA16 DB04 DB11 DB26 EA04 GA08 GA09

Claims (7)

[Claims] 1. A composite rubber ((A) + (B)) comprising (A) a polyorganosiloxane and (B) an alkyl (meth) acrylate rubber, and (C) an aromatic alkenyl compound, an acrylic acid ester, and methacrylic acid. A soft thermoplastic resin molded article obtained by thermoforming a graft copolymer obtained by graft-polymerizing one or more monomers selected from an acid ester and a vinyl cyanide compound. 2. The soft thermoplastic resin molded article according to claim 1, wherein the durometer A hardness measured by a method according to JIS K7215 is 30 to 80. 3. A composite rubber ((A) + (B)) comprising (A) a polyorganosiloxane and (B) an alkyl (meth) acrylate rubber, and (C) an aromatic alkenyl compound, an acrylic acid ester, and methacrylic acid. A soft thermoplastic resin molded article obtained by extrusion molding a graft copolymer obtained by graft-polymerizing one or more monomers selected from an acid ester and a vinyl cyanide compound. 4. A composite rubber ((A) + (B)) comprising (A) a polyorganosiloxane and (B) an alkyl (meth) acrylate rubber, and (C) an aromatic alkenyl compound, an acrylic ester, and methacrylic. A resin molded product obtained by co-extrusion of a hard thermoplastic resin with a graft copolymer obtained by graft polymerization of one or more monomers selected from an acid ester and a vinyl cyanide compound. 5. A composite rubber ((A) + (B)) comprising (A) a polyorganosiloxane and (B) an alkyl (meth) acrylate rubber, and (C) an aromatic alkenyl compound, an acrylate, and a methacryl. Automotive exterior molding parts using a soft thermoplastic resin molded product obtained by thermoforming a graft copolymer obtained by graft-polymerizing one or more monomers selected from acid esters and vinyl cyanide compounds . 6. A composite rubber ((A) + (B)) comprising (A) a polyorganosiloxane and (B) an alkyl (meth) acrylate rubber, is added to (C) an aromatic alkenyl compound, an acrylic ester, and methacrylic acid. An automotive interior skin material using a soft thermoplastic resin molded article obtained by thermoforming a graft copolymer obtained by graft-polymerizing one or more monomers selected from esters and vinyl cyanide compounds. 7. A composite rubber ((A) + (B)) comprising (A) a polyorganosiloxane and (B) an alkyl (meth) acrylate rubber, is added to (C) an aromatic alkenyl compound, an acrylic ester, and methacryl. A building material component using a soft thermoplastic resin molded article obtained by thermoforming a graft copolymer obtained by graft-polymerizing one or more monomers selected from an acid ester and a vinyl cyanide compound.