JP6515703B2 - Method of manufacturing thermoplastic resin molded body, and thermoplastic resin molded body - Google Patents

Description

  The present invention relates to a method for producing a thermoplastic resin molded article, and a thermoplastic resin molded article.

  A molded article made of an acrylic resin is excellent in transparency and has a beautiful appearance and weather resistance, and therefore, is widely used for applications such as electronic parts, vehicle parts, optical parts, ornaments, signs and the like. In particular, acrylic resin molded articles made of an acrylic resin containing a rubber-containing polymer are widely used.

  Such rubber-containing polymers are produced, for example, by an emulsion polymerization method. That is, polybutadiene latex, styrene-butadiene copolymer latex, styrene-butadiene-acrylonitrile copolymer latex, acrylic ester-containing acrylic rubber latex are produced by emulsion polymerization method etc. A powdery polymer is separated and recovered by performing processing such as coagulation, spray drying, or lyophilization. The powdery polymer is usually mixed with a compounding agent as appropriate, melt-kneaded by a single screw extruder or a twin screw extruder, extruded as a strand, and cut by a cold cut method, a hot cut method, etc. It is pelletized. Next, the pellets are supplied to an extruder with a T-die, a molding machine, etc. and processed into an acrylic resin molded body.

  A film-like acrylic resin molded product (hereinafter referred to as "acrylic resin film") is excellent in transparency, weather resistance, flexibility, and processability, and various resin molded products, woodwork products and metal moldings are made. It is laminated on the surface of the goods.

  The acrylic resin film is appropriately modified in the formulation of the acrylic resin composition in order to express physical properties suitable for the application, and therefore, when manufactured using the same extruder, it is washed every formulation It is necessary.

  When molding a melt of an acrylic resin composition with a different formulation, using an extruder, the screw is removed and the extruder is disassembled and cleaned, etc. It is common to remove However, in the production of a small amount of various types, if the decomposition cleaning is performed at each type switching, the productivity is reduced, which leads to an increase in cost.

  As a method of efficiently discharging the previous product from the inside of the extruder without decomposition and cleaning, generally, the melt viscosity of the supplied thermoplastic resin composition is used rather than the melt viscosity of the thermoplastic resin composition in the extruder. It is known that the melt of the thermoplastic resin composition in the extruder can be discharged efficiently if

  In Patent Documents 1 and 2, the step of filling the melt of the low viscosity resin composition into the filter part, and the melt viscosity of the filter part filled with the melt of the low viscosity resin composition are higher than that of the low viscosity resin composition. A process for producing a thermoplastic resin molded article is proposed, which comprises the steps of: supplying a melt of a high viscosity resin composition and filtering and discharging the melt of a low viscosity resin composition.

  However, in the methods proposed in Patent Documents 1 and 2, when it is necessary to switch to a thermoplastic resin composition having a low melt viscosity thereafter, a melt of the thermoplastic resin composition having a high melt viscosity in the extruder is used. There is a problem that problems such as occurrence of defects called fish eyes occur in molded products obtained because a large amount of replacement resin is required because discharge is difficult, and previous molded products can not be discharged sufficiently. The

JP, 2012-228799, A JP, 2013-119200, A

  The present invention relates to a method for producing a thermoplastic resin molded article capable of efficiently discharging the previous product from the inside of the extruder when molding a melt of thermoplastic resin compositions having different compounding formulations using an extruder, and Provided is a thermoplastic resin molded product obtainable by the production method.

The present invention provides the following means [1] to [12].
[1]: A method of producing a thermoplastic resin molded product using an extruder,
The extruder is an extruder formed by discharging the molten material of the thermoplastic resin composition A at a resin temperature T1, and the thermoplastic resin composition A remains inside,
The way is
By supplying the thermoplastic resin composition B to the extruder, the molten resin of the thermoplastic resin composition A remaining in the extruder is discharged from the extruder at a resin temperature T 2 to obtain a thermoplastic resin composition. Characterized in that A is replaced with a thermoplastic resin composition B,
The thermoplastic resin composition A and the thermoplastic resin composition B differ in composition, and
T1 and T2 satisfy | fill the relational expression of following (1) method.
(1) T1 <T2
[2]: The method described in [1] above,
After substituting the thermoplastic resin composition A with the thermoplastic resin composition B, subsequently, the thermoplastic resin composition B is further supplied to the extruder, and the melt of the thermoplastic resin composition B is subjected to resin temperature Including discharging and molding from the extruder at T3 ',
T2 and T3 'satisfy | fill the relational expression of following (2) method.
(2) T2> T3 '
[3]: The method described in [1] above,
After substituting the thermoplastic resin composition A with the thermoplastic resin composition B, subsequently, the thermoplastic resin composition C is further supplied to the extruder, and the thermoplastic resin composition B remaining in the extruder Further replacing the thermoplastic resin composition B with the thermoplastic resin composition C by discharging the molten material from the extruder at a resin temperature T3;
Further supplying the thermoplastic resin composition C to the extruder, and discharging the molten product of the thermoplastic resin composition C from the extruder at a resin temperature T4 for forming;
The thermoplastic resin composition B and the thermoplastic resin composition C differ in composition, and
T3 and T4 satisfy | fill the relational expression of following (3) method.
(3) T3> T4
[4]: A method of producing a thermoplastic resin molded product using an extruder,
Supplying the thermoplastic resin composition A to the extruder, discharging the molten product of the thermoplastic resin composition A from the extruder at a resin temperature T1, and forming the thermoplastic resin molded body;
Discharging the melt of the thermoplastic resin composition A remaining in the extruder from the extruder at a resin temperature T2 by supplying the thermoplastic resin composition B to the extruder;
The thermoplastic resin composition B is further supplied to the extruder, and the melt of the thermoplastic resin composition B is discharged from the extruder at a resin temperature T3 ′ and molded to obtain a further thermoplastic resin molded body When,
Including
The thermoplastic resin composition A and the thermoplastic resin composition B differ in composition, and
A method wherein T1, T2 and T3 'satisfy the following equations (1) and (2).
(1) T1 <T2
(2) T2> T3 '
[5]: A method of producing a thermoplastic resin molded product using an extruder,
Supplying the thermoplastic resin composition A to the extruder, discharging the molten product of the thermoplastic resin composition A from the extruder at a resin temperature T1, and forming the thermoplastic resin molded body;
Discharging the melt of the thermoplastic resin composition A remaining in the extruder from the extruder at a resin temperature T2 by supplying the thermoplastic resin composition B to the extruder;
The thermoplastic resin composition C is further supplied to the extruder, and the molten resin of the thermoplastic resin composition B is discharged from the extruder at a resin temperature T3 to obtain a thermoplastic resin composition of the thermoplastic resin composition B. Further substituting for object C,
The thermoplastic resin composition C is further supplied to the extruder, and the melt of the thermoplastic resin composition C is discharged from the extruder at a resin temperature T4 and molded to obtain a further thermoplastic resin molded body ,
Including
The thermoplastic resin composition A, the thermoplastic resin composition B and the thermoplastic resin composition C differ in composition, and
T1, T2, T3 and T4 satisfy all the relations below.
(1) T1 <T2
(3) T3> T4
[6]: The melt viscosity difference between the thermoplastic resin composition A and the thermoplastic resin composition B at a shear rate of 96 (1 / sec) at a temperature of 240 ° C. is 500 Pa · s or less. The manufacturing method of the thermoplastic resin molded object in any one of 1]-[5].
[7] The melt viscosity difference between the thermoplastic resin composition B and the thermoplastic resin composition C at a shear rate of 96 (1 / sec) at a temperature of 240 ° C. is 500 Pa · s or less. The manufacturing method of the thermoplastic resin molding as described in 3] or [5].
[8] The method for producing a thermoplastic resin molded article according to any one of the above [1] to [7], wherein the thermoplastic resin molded article is a pellet or a film.
[9] The method for producing a thermoplastic resin molded article according to any one of the above [1] to [8], wherein the thermoplastic resin composition is an acrylic resin composition.
[10] The method for producing a thermoplastic resin molded article according to any one of the above [1] to [9], wherein the thermoplastic resin composition is a thermoplastic resin composition containing a rubber-containing polymer.
[11] A thermoplastic resin molded article produced by the production method according to any one of [1] to [10].
[12] A method of replacing a thermoplastic resin composition in an extruder with another thermoplastic resin composition,
The extruder is an extruder formed by discharging the molten material of the thermoplastic resin composition A at a resin temperature T1, and the thermoplastic resin composition A remains inside,
The way is
By supplying the thermoplastic resin composition B to the extruder, the melt of the thermoplastic resin composition A remaining in the extruder is discharged from the extruder at a resin temperature T2, and the thermoplastic resin composition A is discharged. Is replaced with the thermoplastic resin composition B,
The thermoplastic resin composition A and the thermoplastic resin composition B differ in composition, and
T1 and T2 satisfy | fill the relational expression of following (1) method.
(1) T1 <T2

  According to the present invention, when molding a melt of thermoplastic resin compositions different in formulation and formulation using an extruder, a method for producing a thermoplastic resin molded article that efficiently discharges the former type from the inside of the extruder, and the method It is possible to provide a thermoplastic resin molded product obtainable by the production method.

  Hereinafter, although the aspect of the present invention is explained in detail, the scope of the present invention is not restricted by these explanations, and it can be suitably changed and implemented in the range which does not impair the meaning of the present invention except the following illustration.

<Method of Manufacturing Thermoplastic Resin Molding>
According to the present invention, there is provided a method of producing a thermoplastic resin molded product using an extruder,
The extruder is an extruder formed by discharging the molten material of the thermoplastic resin composition A at a resin temperature T1, and the thermoplastic resin composition A remains inside,
The way is
By supplying the thermoplastic resin composition B to the extruder, the molten resin of the thermoplastic resin composition A remaining in the extruder is discharged from the extruder at a resin temperature T 2 to obtain a thermoplastic resin composition. Characterized in that A is replaced with a thermoplastic resin composition B,
The thermoplastic resin composition A and the thermoplastic resin composition B differ in composition, and
T1 and T2 satisfy the following equation (1):
(1) T1 <T2
Is provided. Here, the thermoplastic resin composition B may be a composition for further efficiently substituting for another thermoplastic resin composition C, or a molded body is obtained from the thermoplastic resin composition B itself. It may be a composition for In one embodiment of the present invention, in the above formula, (1) can be T1 + 5 ° C. ≦ T2.

In the method of the present invention, as an embodiment of obtaining a molded body from the thermoplastic resin composition B itself, after substituting the thermoplastic resin composition A with the thermoplastic resin composition B, subsequently, the thermoplastic resin composition B is The method may further include: feeding the melt of the thermoplastic resin composition B from the extruder at a resin temperature T3 ′ and forming the melt by further feeding the extruder.
T2 and T3 ′ satisfy the following equation (2):
(2) T2> T3 '
It may be In one embodiment of the present invention, in the above formula, (2) can satisfy T2−5 ° C. ≧ T3 ′.

In the method of the present invention, the thermoplastic resin composition A may be used as a thermoplastic resin composition as an embodiment in which substitution with the thermoplastic resin composition C is further streamlined to obtain a molded body from the thermoplastic resin composition C. After replacing with B, the thermoplastic resin composition C is further supplied to the extruder, and the melt of the thermoplastic resin composition B remaining in the extruder is discharged from the extruder at a resin temperature T3. Further replacing the thermoplastic resin composition B with the thermoplastic resin composition C;
The method may further include supplying the thermoplastic resin composition C to the extruder, and discharging the molten product of the thermoplastic resin composition C from the extruder at a resin temperature T4 for molding.
The thermoplastic resin composition B and the thermoplastic resin composition C differ in composition, and
T3 and T4 satisfy the following equation (3):
(3) T3> T4
It may be In one embodiment of the present invention, in the above formula, (3) can satisfy T3-5 ° C. ≧ T4.

According to the present invention, after a molded body is produced from the thermoplastic resin composition A, the composition A remaining in the extruder is discharged by the thermoplastic resin composition B, and the molded body is produced from the thermoplastic resin composition B. Methods of making are provided. Specifically, according to the present invention, it is a method of producing a thermoplastic resin molded product using an extruder,
(Α) Supplying the thermoplastic resin composition A to the extruder, discharging the molten product of the thermoplastic resin composition A from the extruder at a resin temperature T1, and forming the thermoplastic resin molded body,
(A) discharging the melt of the thermoplastic resin composition A remaining in the extruder from the extruder at a resin temperature T2 by supplying the thermoplastic resin composition B to the extruder;
(B) The thermoplastic resin composition B is further supplied to the extruder, and the melt of the thermoplastic resin composition B is discharged from the extruder at a resin temperature T3 ′ and molded, and a further thermoplastic resin molded body To get
Including
The thermoplastic resin composition A and the thermoplastic resin composition B differ in composition, and
T1, T2 and T3 'satisfy the following equations (1) and (2):
(1) T1 <T2
(2) T2> T3 '
Is provided. In one embodiment of the present invention, in the above formula, (1) can be T1 + 5 ° C. ≦ T2, and (2) can be T2-5 ° C. ≧ T3 ′.

According to the present invention, there is provided an extruder formed by discharging a molten material of a thermoplastic resin composition A, wherein the thermoplastic resin composition B remains in the interior of the thermoplastic resin composition B. Thus, a method is provided for discharging the residual thermoplastic resin composition A from the extruder and then producing a molded body from the thermoplastic resin composition B. Specifically, according to the present invention, it is a method of producing a thermoplastic resin molded product using an extruder,
The extruder is an extruder formed by discharging a molten material of the thermoplastic resin composition A, and the thermoplastic resin composition A remains inside,
The way is
(A) discharging the melt of the thermoplastic resin composition A remaining in the extruder from the extruder at a resin temperature T2 by supplying the thermoplastic resin composition B to the extruder;
(B) The thermoplastic resin composition B is further supplied to the extruder, and the melt of the thermoplastic resin composition B is discharged from the extruder at a resin temperature T3 ′ and molded to form a thermoplastic resin molded body To get
Including
The thermoplastic resin composition A and the thermoplastic resin composition B differ in composition, and
T1, T2 and T3 'satisfy the following equations (1) and (2):
(1) T1 <T2
(2) T2> T3 '
Is provided. In one embodiment of the present invention, in the above formula, (1) can be T1 + 5 ° C. ≦ T2, and (2) can be T2-5 ° C. ≧ T3 ′.

<Thermoplastic resin composition>
In the following description, "the thermoplastic resin composition" may be referred to as "the thermoplastic resin composition A", "the thermoplastic resin composition B", and "the thermoplastic resin composition C". At this time, the thermoplastic resin compositions A and B differ in composition, the thermoplastic resin compositions B and C differ in composition, and the thermoplastic resin compositions A and C differ in composition.

  As a thermoplastic resin composition which can be used in the present invention, for example, rubber, reinforced styrene resin such as polystyrene, high impact polystyrene, medium impact polystyrene, styrene-acrylonitrile copolymer (SAN resin), acrylonitrile-butyl acrylate Rubber-styrene copolymer (AAS resin), acrylonitrile-ethylenepropyl rubber-styrene copolymer (AES), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS), ABS resin (for example, acrylonitrile-butadiene-styrene copolymer) Styrene resins such as combined, acrylonitrile-butadiene-styrene-alphamethylstyrene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene copolymer); Acrylic resins such as methacrylate (PMMA); olefin resins such as low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP); polyvinyl chlorides such as polyvinyl chloride and polyvinylidene chloride; ethylene Vinyl chloride-based copolymer resins such as vinyl chloride-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, etc .; Polyester-based resins such as polyethylene terephthalate (PETP, PET), polybutylene terephthalate (PBTP, PBT), etc .; polycarbonate (PC), Polycarbonate resins such as modified polycarbonate; Polyamide resins such as polyamide 66, polyamide 6, polyamide 46; Polyacetal (POM) resins such as polyoxymethylene copolymer, polyoxymethylene homopolymer; Dinning resins, super engineering resins such as polyethersulfone (PES), polyetherimide (PEI), thermoplastic polyimide (TPI), polyetherketone (PEK), polyetheretherketone (PEEK), polyphenylene sulfide (PSU) And cellulose derivatives such as cellulose acetate (CA), cellulose acetate butyrate (CAB) and ethyl cellulose (EC), liquid crystal polymers, and liquid crystal polymers such as liquid crystal aromatic polyesters. Also, thermoplastic polyurethane elastomer (TPU), thermoplastic styrene butadiene elastomer (TSBC), thermoplastic polyolefin elastomer (TPO), thermoplastic polyester elastomer (TPEE), thermoplastic vinyl chloride elastomer (TPVC), thermoplastic polyamide elastomer (TPAE) Etc.) can also be used. In the present embodiment, a blend of one or more thermoplastic resin compositions may be used, or additives may be used.

  The thermoplastic resin composition that can be used in the present invention is preferably an acrylic resin composition that is required to have qualities such as transparency and weather resistance. In particular, an acrylic resin molded article which is required to have transparency, weatherability, flexibility, processability and the like can be particularly suitably used as a thermoplastic resin composition because it contains a rubber-containing polymer which is easily scorched.

<Acrylic resin composition>
As used herein, "alkyl acrylate" and "alkyl methacrylate" refer to alkyl esters of acrylic acid and alkyl esters of methacrylic acid, respectively. Also herein, "(meth) acrylic" means acrylic and / or methacrylic. Further herein, "alkyl (meth) acrylate" means alkyl acrylate and / or alkyl methacrylate.

  The acrylic resin composition that can be used in the present invention is not particularly limited except that it contains alkyl (meth) acrylate as a main component. Moreover, you may contain the rubber containing polymer mentioned later.

  The acrylic resin composition that can be used in the present invention can include a thermoplastic polymer. As a thermoplastic polymer, an alkyl methacrylate unit having an alkyl group having 1 to 4 carbon atoms in an amount of 50 to 100% by mass and at least one other vinyl monomer copolymerizable therewith, as a monomer unit The thermoplastic polymer which contains 50 mass% and whose reduced viscosity of a polymer is 0.1 L / g or less can be mentioned. The reduced viscosity can be measured by a known method. For example, 0.1 g of a polymer can be dissolved in 100 mL of chloroform and measured at 25 ° C. The content of the alkyl methacrylate unit is preferably 70 to 100% by mass. The thermoplastic polymer preferably has a glass transition temperature of 80 to 110 ° C. As a specific example of such a thermoplastic polymer, Mitsubishi Rayon Co., Ltd. "Acrypet VH", "Acrypet MD", "Acrypet MF" (all are brand names) etc. are mentioned, for example.

<Rubber-containing polymer>
The thermoplastic resin composition that can be used in the present invention can contain a rubber-containing polymer. The rubber-containing polymer is preferably a rubber-containing polymer (G) shown below.

<Outline of Method of Producing Rubber-Containing Polymer (G)>
The rubber-containing polymer (G) is produced by polymerizing a monomer component (a) containing 30% by mass or more of alkyl acrylate with respect to all monomer units to produce a rubber polymer (A); It can be set as the polymer manufactured through the process of polymerizing the monomer component (b) which contains 51 mass% or more of alkyl methacrylates in presence of this rubber polymer (A). It is preferable that a monomer component (a) is a component from which the glass transition temperature (Tg) of the polymer obtained by superposing | polymerizing it independently will be -50-25 degreeC. Moreover, it is preferable that a monomer component (b) is a component from which the glass transition temperature (Tg) of the polymer obtained by superposing | polymerizing it independently will be 70-120 degreeC.

  The step of emulsion-polymerizing the component (s) prior to the polymerization of the monomer component (a), wherein the component (s) is obtained by polymerizing it alone and the Tg of the polymer obtained is 70 to 120 ° C. The emulsion polymerization step can be carried out. In addition, between the emulsion polymerization step of the monomer component (a) and the emulsion polymerization step of the monomer component (b), a step of emulsion polymerization of the monomer component (c) and the like may be performed as necessary. Can.

  The ratio of the content of the rubber-containing polymer (G) to the thermoplastic polymer in the acrylic resin composition is preferably about 95: 5 to 5:95 (parts by mass).

<Method of producing rubber-containing polymer (G)>
First, the monomer component of the rubber-containing polymer (G) will be described, and then a specific method for producing the polymer will be described.

<Monomer component (a)>
The monomer component (a) is a monomer mixture containing 30% by mass or more of alkyl acrylate with respect to the total amount of monomers, and in the case of carrying out a multistage polymerization process, a raw material for the first polymerization process The monomer mixture to be The rubber polymer (A) is produced by polymerizing the monomer component (a) as a raw material.

  The alkyl acrylate (hereinafter sometimes referred to as "monomer (a1)") may be linear or branched. Methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate Can be mentioned. Of these, n-butyl acrylate is preferred. The alkyl acrylates can be used alone or in combination of two or more.

  As monomers other than alkyl acrylate in monomer component (a), alkyl methacrylate (hereinafter sometimes referred to as "monomer (a2)"), a double bond copolymerizable with these Other monomers having one (hereinafter sometimes referred to as “monofunctional monomer (a3)”), and polyfunctional monomers (hereinafter “polyfunctional monomer (a4) And the like. Monomers other than the alkyl acrylate in monomer component (a) can be used individually or in mixture of 2 or more types.

  Examples of the alkyl methacrylate include linear or branched alkyl groups. Specific examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, and t-butyl methacrylate . The alkyl methacrylates can be used alone or in combination of two or more.

  Examples of the monofunctional monomer (a3) include acrylic monomers such as alkoxy acrylate, cyanoethyl acrylate, acrylamide and (meth) acrylic acid; and aromatic vinyl monomers such as styrene and alkyl substituted styrene And vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. The monofunctional monomers (a3) can be used alone or in combination of two or more.

  Examples of the polyfunctional monomer (a4) include crosslinkable monomers having two or more copolymerizable double bonds in one molecule, and the following may be mentioned as specific examples. Di (meth) acrylics such as ethylene glycol di (meth) acrylate, 1,3- butylene glycol di (meth) acrylic acid, 1,4- butylene glycol di (meth) acrylic acid, propylene glycol di (meth) acrylic acid Acid alkylene glycol; polyvinylbenzene such as divinylbenzene and trivinylbenzene; and cyanurate monomers such as triallyl cyanurate and triallyl isocyanurate; α, β-unsaturated carboxylic acids or dicarboxylic acids such as allyl methacrylate Allyl, methallyl or crotyl ester and the like. A polyfunctional monomer (a4) can be used individually or in mixture of 2 or more types.

  The content of alkyl acrylate in the monomer component (a) is preferably 30 to 99.9% by mass. The content of alkyl methacrylate in the monomer component (a) is preferably 0 to 69.9% by mass. The content of monofunctional monomer (a3) in monomer component (a) is preferably 0 to 20% by mass. The content of the polyfunctional monomer (a4) in the monomer component (a) is preferably 0.1 to 10% by mass.

  The glass transition temperature (hereinafter referred to as “Tg”) of the rubber polymer (A) is preferably −50 ° C. or higher, for example, from the viewpoint of flexibility in film applications and impact resistance in impact strength modifier applications. 25 ° C. or less. In the present invention, Tg is a value calculated from the formula of FOX using the value described in Polymer Handbook [Polymer HandBook (J. Brandrup, Interscience, 1989)]. In addition, the content of the rubber polymer (A) in the rubber-containing polymer (G) is, for example, the film-forming property of the rubber-containing polymer (G) in film applications and the rubber-containing polymer in impact strength modifier applications From the viewpoint of the impact resistance of the resin molded body to which (G) is added, the content is preferably 5 to 70% by mass.

  The monomer component (a) in the rubber-containing polymer (G) may be polymerized in two or more stages.

<Monomer component (b)>
The monomer component (b) is a monomer mixture to be a raw material of the final stage polymerization when carrying out the multistage polymerization process, and the formability of the rubber-containing polymer (G), and / or the machine Component involved in As the alkyl methacrylate in the monomer component (b), one or more monomers selected from the group consisting of the monomers listed as the “monomer (a2)” in the description of the monomer component (a) A mer can be used. As monomers other than alkyl methacrylate in monomer component (b), alkyl acrylate and other monomers having one double bond copolymerizable with these (hereinafter referred to as There may be mentioned “monofunctional monomer (b3)”. As the alkyl acrylate, one or more monomers selected from the group consisting of the monomers listed as "monomer (a1)" can be used. As a monofunctional monomer (b3), 1 or more types of monomers selected from the group which consists of a monomer mentioned as "monofunctional monomer (a3)" can be used. The step of emulsion polymerization of the monomer component (b) can be performed in two or more stages.

  The content of alkyl methacrylate in the monomer component (b) is preferably 51 to 100% by mass. The content of alkyl acrylate in the monomer component (b) is preferably 0 to 20% by mass. The content of the monomer (b3) in the monomer component (b) is preferably 0 to 49% by mass.

  The use amount of the monomer component (b) accounts for 100% by mass of the total of the monomer components used in all steps of the polymerization method, for example, the film forming property of the rubber-containing polymer (G) in film application And from the viewpoint of the impact resistance of the resin molded product to which the rubber-containing polymer (G) is added in the impact strength modifier application, the content is preferably 30 to 95% by mass.

<Monomer component (s)>
Prior to the step of producing the rubber polymer (A) by polymerizing the monomer component (a), the component (s) which is obtained by polymerizing the monomer alone and which has a Tg of 70 to 120 ° C. is emulsified. A step of polymerizing can be included. As a monomer component (s), the same thing as a monomer component (b) can be mentioned.

<Monomer component (c)>
Between the step of polymerizing the monomer component (a) to produce the rubber polymer (A) and the step of polymerizing the monomer component (b) in the presence of the rubber polymer (A) And emulsion polymerization of the monomer component (c). As monomer component (c), 9.9 to 90% by mass of alkyl acrylate, 0 to 90% by mass of alkyl methacrylate, and other monomers 0 to 1 having one double bond copolymerizable therewith A mixture containing 20% by mass and 0.1 to 10% by mass of the polyfunctional monomer may be mentioned. Other monomers and polyfunctional monomers used here include the above-mentioned monofunctional monomer (a3) and multifunctional monomer (a4).

  The step of emulsion polymerization of the monomer component (c) can be performed in two or more stages. In the case of polymerization in two or more stages, the composition of the monomer component (c) may be the same or different. The monomer component (c) may contain a surfactant, and may be further mixed with water and stirred to be supplied as an emulsion into the polymerization vessel.

<Polymerization method>
Examples of the method for producing the rubber-containing polymer (G) include sequential multistage emulsion polymerization. As a method of polymerizing in three steps, a monomer component (a) for obtaining a rubbery polymer (A), water and a surfactant are mixed to be in the form of an emulsion and supplied into a polymerization vessel for polymerization. Then, the monomer component (c) is supplied into the polymerization container and polymerized, and the monomer component (b), water and surfactant are mixed to form an emulsion and supplied into the polymerization container. And polymerization methods. In addition, the process of supplying and polymerizing a monomer component (c) in a superposition | polymerization container is a process performed as needed, and may superpose | polymerize in two steps. That is, the rubber-containing polymer (G) is supplied into the polymerization container in the state of an emulsion by mixing the monomer component (a) for obtaining the rubbery polymer (A), water and surfactant. After polymerization and polymerization, the monomer component (b), water and a surfactant may be mixed to form an emulsion, which may be supplied into the polymerization vessel and polymerized.

  The polymer product obtained by using the rubber-containing polymer (G) produced by the above method has an advantage that the coarse particles in the finally obtained polymer latex are small. In particular, when the polymer product is a film, it is preferable in that it has less fish eyes.

  As surfactant used when manufacturing by a sequential multistage emulsion polymerization method, surfactant of anionic type, cationic type, and nonionic type is mentioned, for example. These can be used alone or in combination of two or more. Examples of anionic surfactants include the following. Rosin soap, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinic acid, etc., sulfate salt such as sodium lauryl sulfate, etc .; sodium dioctyl sulfosuccinate, dodecyl benzene Sulfonic acid salts of sodium sulfonate, sodium of alkyl diphenyl ether disulfonate, etc .; and phosphoric acid ester salts of sodium polyoxyethylene alkylphenyl ether phosphate, sodium of polyoxyethylene alkyl ether phosphate etc. As a specific example of the commercial item of anionic surfactant, the thing of the following brand names is mentioned, for example. Sanyo Chemical Industries, Ltd. Eleminol NC-718, Toho Chemical Industry Co., Ltd. phosphanol LO-529, phosphanol RS-610NA, phosphanol RS-620NA, phosphanol RS-630NA, phosphanol Fanol RS-640NA, phosphanol RS-650NA and phosphanol RS-660NA, and Latem P-044, Latem P-0405, Latem P-0406 and Latem P-0407 manufactured by Kao Corporation.

  As a method of preparing an emulsion liquid by mixing a monomer component, water, and surfactant, the method of the following (i)-(iii) is mentioned, for example. (I) A method of charging a surfactant after charging a monomer component in water, (ii) A method of charging a monomer component after charging a surfactant in water, and (iii) monomer A method in which water is added after the surfactant has been added to the ingredients.

  As a mixing apparatus for mixing the monomer component with water and a surfactant to prepare an emulsion, for example, a stirrer equipped with a stirring blade; a forced emulsification apparatus such as a homogenizer, a homomixer, etc .; and a membrane emulsification apparatus It can be mentioned.

  As the above emulsion, either water-in-oil (W / O) type in which water droplets are dispersed in oil of monomer component, or oil-in-water (O / W) type in which oil droplets of monomer component are dispersed in water Dispersions of can also be used. The diameter of the oil droplet of the O / W type and the dispersed phase is preferably 100 μm or less, more preferably 50 μm or less, and particularly preferably 15 μm or less.

  The amount of surfactant used for preparation of the above-mentioned emulsion liquid shall be 0.5 mass part or more and 1.6 mass parts or less, when the total amount of the monomer component in all the stages of polymerization is 100 mass parts. desirable. In the particle size adjustment of the stepwise multistage polymer, the particle size is usually adjusted by the amount of the surfactant used in the first stage. However, in the present invention, the amount of surfactant used can be reduced by adding the surfactant to water (aqueous medium) previously charged in the polymerization vessel, separately from the surfactant added to the monomer component. The particle diameter of the rubber-containing polymer can be reduced.

  As a polymerization initiator and a chain transfer agent to be used when polymerizing the monomer component (a) and the monomer component (b), or when polymerizing the monomer component (c), known ones are known. It can be used. Examples of the method of adding the polymerization initiator and the chain transfer agent include a method of adding to either one of the aqueous phase and the monomer phase, or a method of adding to both phases.

  Examples of the polymerization initiator include peroxides, azo initiators and redox initiators. The redox initiator is an initiator in which a peroxide and an oxidizing agent or a reducing agent are combined, and an initiator in which an azo initiator and an oxidizing agent or a reducing agent are combined, and specific examples of the redox initiator are And sulfoxylate initiators in which ferrous sulfate, disodium ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate and hydroperoxide are combined.

  As a chain transfer agent, C2-C20 alkyl mercaptan, mercapto acids, thiophenol and carbon tetrachloride are mentioned, for example. These can be used alone or in combination of two or more. For example, n-octyl mercaptan is mentioned.

  As a method for producing a latex of a rubber-containing polymer (G), a monomer component (a), water and a surfactant are mixed to be in the form of an emulsion, supplied into a reactor and polymerized, and then a single amount Method in which body component (c) is supplied into the reactor for polymerization, and further, monomer component (b), water and surfactant are mixed to form an emulsion and supplied into the reactor for polymerization And the method of manufacturing. In this case, after the aqueous solution in the reactor containing ferrous sulfate, disodium ethylenediaminetetraacetate and sodium formaldehyde sulfoxylate dihydrate is heated up to the polymerization temperature, the monomer component (a), water The emulsion obtained by mixing the surfactant and the surfactant is supplied into the reactor for polymerization, and then the monomer component (c) is supplied into the reactor for polymerization, and the monomer component (b), water and The method of supplying the emulsion liquid which mixed surfactant with a reactor, and superposing | polymerizing is preferable. Here, the step of supplying the monomer component (c) into the reactor for polymerization is an optional step and can be omitted from the method for producing the latex of the rubber-containing polymer (G) of the present invention.

  The polymerization temperature for obtaining the latex of the rubber-containing polymer (G) is, for example, about 40 to 120 ° C. although it varies depending on the type and amount of the polymerization initiator and the like used.

  The latex of the rubber-containing polymer (G) obtained by the above-mentioned method can be treated using a filtration device provided with a filter medium as required.

  The latex of the rubber-containing polymer (G) thus obtained can be used in various applications in the form of a latex. In addition, the rubber-containing polymer (G) is recovered from the latex by a known method such as salting out coagulation, acid precipitation coagulation, freeze coagulation or spray drying, and dried to obtain a rubber-containing polymer ( It can be used as a powder of G). Furthermore, this powder can be melt extruded and pelletized for use.

  When recovering the rubber-containing polymer (G) by a coagulation method by salting out using a metal salt, the residual metal content in the finally obtained rubber-containing polymer (G) should be 800 ppm or less The residual metal content is preferably as small as possible.

<Additives>
In the acrylic resin composition of the present invention, if necessary, compounding agents such as, for example, stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, foaming agents, fillers, colorants, UV absorbers, etc. Can be included.
In particular, when the acrylic resin molded product is an acrylic resin film and is used as a protective layer of a substrate, it is preferable that a UV absorber is contained in the acrylic resin composition to impart weather resistance. The type of the UV absorber is not particularly limited, but benzotriazole UV absorbers having a molecular weight of 400 or more and triazine UV absorbers having a molecular weight of 400 or more are particularly preferable. Commercial products of the former include, for example, trade name Tinuvin 234 of Ciba Specialty Chemicals Ltd., trade name Adekastab LA-31 of ADEKA Co., Ltd., and commercial products of the latter include, for example, Ciba Specialty Chemicals ( Trade name Tinuvin 1577, trade name Adekastab LA-46 etc.

  The amount of the ultraviolet absorber added is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin constituting the acrylic resin molded body. From the viewpoint of the weather resistance, it is more preferably 0.5 parts by mass or more, particularly preferably 1 part by mass or more. On the other hand, it is more preferably 5 parts by mass or less and particularly preferably 3 parts by mass or less from the viewpoint of preventing process contamination during film formation and the transparency of the molded product.

  In particular, it is preferable that the acrylic resin composition contains a light stabilizer. Although a well-known thing can be used as a light stabilizer, Especially radical scavengers, such as a hindered amine light stabilizer, are preferable. As a commercial item of such a light stabilizer, Adekastab LA-57, Adekastab LA-67, Sanol LS-770 of ADEKA, CHIMASSORB 2020FDL of BASF, CHIMASSORB 944 FDL etc. (the brand name) etc. are mentioned.

  As for content of a hindered amine light stabilizer, 0.1-5 mass parts is preferable with respect to 100 mass parts of resin which comprises an acrylic resin molded object. From the viewpoint of light resistance, more preferably 0.2 parts by mass or more. On the other hand, it is more preferably 2 parts by mass or less, particularly preferably 1.5 parts by mass or less from the viewpoint of preventing process contamination during film formation.

<Extruder>
As an extruder which can be used for this invention, general apparatuses, such as uniaxial, same direction two axes, different direction two axes, etc. are mentioned, for example.
When the thermoplastic resin molded product is a pellet to be described later, a preferable extruder is an apparatus having a large kneading effect such as a twin-screw kneading extruder. As a preferable twin-screw extruder, TEM machine by Toshiba Machine Co., Ltd. etc. is mentioned. In addition, as a screw configuration, a thermoplastic resin composition such as a conveying portion that conveys a thermoplastic resin composition, a kneading zone, and a screw segment (screw segment having a reverse spiral winding direction) in which the feeding direction of the melt is opposite A screw configuration having a kneading section for kneading can be mentioned.

  The extruder is preferably one having a vent capable of degassing the moisture in the thermoplastic resin composition as the raw material and the volatile gas generated from the melt-kneaded melt. At the vent, a pressure reducing pump such as a vacuum pump is preferably installed. By such installation, generated moisture and volatile gas are efficiently discharged to the outside of the extruder. It is also possible to install a screen for removing foreign matter and the like mixed in the extruded raw material in a zone in front of the die part of the extruder, and remove the foreign matter from the thermoplastic resin composition. As such a screen, a filter pack, a screen changer, a leaf disc filter and the like using a wire mesh, a sintered metal non-woven fabric and the like are exemplified.

  Further, as a method of increasing the kneading effect, it is also possible to increase the number of rotations of the screw as much as possible and reduce the supply amount of the thermoplastic resin composition, and thus the thermoplastic resin composition melt-extruded is Shear heat generation tends to occur, and the temperature at the head tends to increase. The melt melt-kneaded in the extruder is extruded as a strand from a die having a nozzle with a diameter of about 3 to 5 mm installed in the head, and cut by a cold cut method or a hot cut method to be pelletized .

<Resin temperature>
The resin temperature of the present invention indicates the resin temperature of the melt of the thermoplastic resin composition measured by the head portion of the extruder. The resin temperature is not particularly limited as long as it can melt the thermoplastic resin composition.

  When the thermoplastic resin composition is the above-mentioned acrylic resin composition or contains the above-mentioned rubber-containing polymer, if the resin temperature is 200 ° C. or higher, the melt extrusion becomes easy and the productivity becomes good, 280 C. or less, thermal degradation of the acrylic resin composition is difficult to progress, so that occurrence of fish eyes and the like can be suppressed, and a thermoplastic resin molded article having a good appearance can be obtained.

  In the method for producing a thermoplastic resin molded product of the present invention, the relational expression (1) T1 <T2 is satisfied between the resin temperature T1 and the resin temperature T2. In the method for producing a thermoplastic resin molded article of the present invention, it is preferable that the formula (1) satisfies the relational expression of T1 + 5 ° C. ≦ T2, preferably T1 + 10 ° C. ≦ T2, and T1 + 15 ° C. ≦ T2. It is more preferable that T1 + 20 ° C. ≦ T2 is more preferable.

  By setting the resin temperature T2 higher than the resin temperature T1, the melt viscosity of the thermoplastic resin composition A and the thermoplastic resin composition B becomes low, and the melt viscosity difference between the wall surface and the center in the extruder due to the shear rate Is considered to be small, and the thermally deteriorated material of the thermoplastic resin composition A retained on the wall surface in the extruder can be efficiently discharged. Therefore, the resin amount of the thermoplastic resin composition B necessary to discharge the thermally deteriorated product of the thermoplastic resin composition A can be reduced.

  In the method for producing a thermoplastic resin molded product of the present invention, the relational expression (2) T2> T3 'is satisfied between the resin temperature T2 and the resin temperature T3'. In the method for producing a thermoplastic resin molded product of the present invention, it is preferable to satisfy the relational expression of (2) T2-5 ° C.TT3 ′, preferably T2-10 ° C. ≧ T3 ′, T2-15 ° C. ≧ It is more preferable that it is T3 ', and it is still more preferable that it is T2-20 degreeC> = T3'. By setting the resin temperature T3 ′ to be lower than the resin temperature T2, in the step of molding the melt of the thermoplastic resin composition B, the generation of the thermally deteriorated material of the thermoplastic resin composition B with time can be suppressed. .

  In the method for producing a thermoplastic resin molded product of the present invention, it is preferable to satisfy the relational expression of T1 <T3 between the resin temperature T1 and the resin temperature T3. In the method for producing a thermoplastic resin molded article of the present invention, it is preferable to satisfy the relational expression of T1 + 5 ° C ≦ T3, preferably T1 + 10 ° C ≦ T3, more preferably T1 + 15 ° C ≦ T3, and more preferably T1 + 20 ° C ≦ More preferably, it is T3. By making the resin temperature T3 higher than the resin temperature T1, it is considered that the melt viscosity of the thermoplastic resin composition in the extruder decreases, and the difference in the melt viscosity between the wall and the center in the extruder due to the shear rate decreases. , The former type in the extruder can be discharged efficiently. Therefore, it is possible to reduce the amount of resin of the thermoplastic resin composition required to discharge the previous product.

  In the method for producing a thermoplastic resin molded product of the present invention, the relational expression (3) T3> T4 is satisfied between the resin temperature T3 and the resin temperature T4. In the method for producing a thermoplastic resin molded product of the present invention, it is preferable to satisfy the relational expression of (3) T3-5 ° C. ≧ T4, preferably T3-10 ° C. ≧ T4, and T3-15 ° C. ≧ T4. It is more preferable that T3 −20 ° C. ≧ T4. By setting the resin temperature T4 to be lower than the resin temperature T3, in the step of molding the melt of the thermoplastic resin composition C, it is possible to suppress the generation of the thermally deteriorated material of the thermoplastic resin composition C with time.

Melt viscosity
The melt viscosity of the present invention indicates the melt viscosity of the thermoplastic resin composition at a shear rate of 96 (1 / sec) at a temperature of 240 ° C.

  The melt viscosity difference between the thermoplastic resin composition A and the thermoplastic resin composition B that can be used in the present invention at a shear rate of 96 (1 / sec) at a temperature of 240 ° C. is 500 Pa · s or less It is preferable that the pressure is 300 Pa · s or less, more preferably 200 Pa · s or less.

  The melt viscosity difference between the thermoplastic resin composition B and the thermoplastic resin composition C that can be used in the present invention at a shear rate of 96 (1 / sec) at a temperature of 240 ° C. is 500 Pa · s or less It is preferable that the pressure is 300 Pa · s or less, more preferably 200 Pa · s or less. The melt viscosity difference between the thermoplastic resin composition A and the thermoplastic resin composition B, and / or the melt viscosity difference between the thermoplastic resin composition B and the thermoplastic resin composition C, may be 500 Pa · s or less For example, even in multi-variety production, it can be carried out without reducing the productivity.

<Thermoplastic resin molding>
As a thermoplastic resin molded object obtained by this invention, although a pellet, a film, a lamination film, a sheet etc. are mentioned, for example, if it is a thermoplastic resin molded object using an extruder, it will not be limited in particular.

<Film>
When the thermoplastic resin molded product obtained by the present invention is a film, it can be produced by a known method such as melt casting, T-die method, inflation method, etc., but from the economical point of view the T-die method preferable.

  When a film is formed by the T-die method, the surface smoothness of the obtained film is improved by using a method of forming a film by sandwiching a plurality of rolls or belts selected from metal rolls, nonmetal rolls and metal belts. In addition, it is possible to suppress print omission when printing on a film. As the metal roll, a mirror surface touch roll made of metal described in Japanese Patent No. 2808251, or a sleeve touch method including a metal sleeve (metal thin film pipe) described in WO97 / 28950 and a forming roll are used. Can be exemplified. Moreover, as a nonmetallic roll, touch rolls, such as silicone rubber, etc. can be illustrated. Furthermore, as a metal belt, a metal endless belt etc. can be illustrated. A plurality of these metal rolls, non-metal rolls and metal belts can be used in combination.

  In the method of forming a film by sandwiching a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts as described above, the thermoplastic resin composition after melt extrusion is substantially banked (resin It is preferable to form a film by surface transfer without being substantially rolled, while holding in a state where there is no stagnation. When forming a film without forming a bank (resin reservoir), the thermoplastic resin composition in the cooling process is surface-transferred without rolling, so the heat shrinkage of the film formed by this method is reduced. You can also

  In addition, when melt-extruding by T-die method etc., it is also preferable to filter and extrude the thermoplastic resin composition in a molten state with a screen mesh of 200 mesh or more from the viewpoint of the fisheye reduction in a film.

<Laminated film>
Moreover, when the thermoplastic resin molding obtained by this invention is a film, another resin can be laminated | stacked on the surface of a film. For example, when the surface hardness is required, it is preferable to use an acrylic resin having a high surface hardness. Specifically, by using an acrylic resin having a pencil hardness (measured according to JIS K 5400) of 2H or more, an acrylic resin laminate film having mold whitening resistance, surface hardness (scratch resistance), and heat resistance can be obtained. Therefore, it is preferable.

  Further, from the viewpoint of improving the weather resistance and the solvent resistance, a fluorine resin may be laminated. The type of the fluorine-based resin is not particularly limited, and known fluorine-based resins can be used. Specifically, vinylidene fluoride polymers, vinylidene fluoride and fluorine compounds such as vinyl fluoride and tetrafluoroethylene, or acrylic monomers such as acrylic acid alkyl esters and methacrylic acid alkyl esters and vinylidene fluoride The resin composition which has a copolymer or a vinylidene fluoride polymer as a main component is mentioned.

  This fluorocarbon resin layer may, if necessary, be a common compounding agent, for example, a stabilizer, a lubricant, a processing aid, a plasticizer, an impact modifier, a foaming agent, a filler, an antibacterial agent, an antifungal agent, a release agent And antistatic agents, colorants, matting agents, ultraviolet light absorbers, light stabilizers and the like.

<Thickness of film>
When the thermoplastic resin molded product obtained by the present invention is a film, the thickness of the film is preferably 300 μm or less. As for the thickness, when using for a lamination-molded article, 50 micrometers-300 micrometers are preferable. When the thickness is 50 μm or more, a sufficient depth can be obtained in the appearance of a molded article. In particular, when forming into a complicated shape, sufficient thickness can be obtained by stretching. On the other hand, when the thickness is 300 μm or less, it has appropriate rigidity, so that the laminateability, the secondary processability and the like are improved. Also, in terms of mass per unit area, it is economically advantageous. Furthermore, the film forming property is stabilized and the production of the film becomes easy.

In addition, the film of the present invention can be subjected to surface treatment for imparting various functions, as necessary. The surface treatment includes printing such as silk printing and inkjet printing, metal deposition for imparting metallic tone or metal, sputtering, wet plating, surface hardening for improving surface hardness, and water repellency for preventing soiling. And antistatic treatment for the purpose of dust adhesion prevention or electromagnetic wave cutting, anti-reflection layer formation, anti-glare treatment and the like.
Among the processes described above, when printing is to be performed, it is preferable to perform one-side printing on the film, and among them, backside printing in which the printing surface is disposed on the adhesive surface with the base resin protects the printing surface It is particularly preferable in terms of imparting feeling.

<Laminated body of film and substrate>
Also, the film of the present invention can be laminated to a substrate. For example, if an acrylic resin film is used as it is transparent and laminated on a substrate, it can be used as a substitute for clear coating, and the color tone of the substrate can be utilized. As described above, in applications where the color tone of the base material is to be utilized, the acrylic resin film is superior to polyvinyl chloride film and polyester film in terms of transparency, depth feeling and luxury feeling.

  As a base material on which an acrylic resin film is laminated, various resin molded articles, woodworking products and metal molded articles may be mentioned. Further, among the resin molded products, as a resin constituting a thermoplastic resin molded product which can be melt-adhered to an acrylic resin film, ABS resin, AS resin, polystyrene resin, polycarbonate resin, polyvinyl chloride resin, acrylic resin, polyester resin Or the resin which has these as a main component is mentioned. Among these, ABS resin, AS resin, polycarbonate resin, vinyl chloride resin, or a resin containing these resins as a main component is preferable in terms of adhesiveness. In addition, it is possible to adhere an acrylic resin film and a base material by using an adhesive layer even if base resin which is hard to melt and adhere such as polyolefin resin is used.

  When an acrylic resin film is laminated on a thin, substantially two-dimensional base material, the base material capable of heat fusion can be bonded by a known method such as thermal lamination. Moreover, with respect to the base material which is not heat-seal | fused, it can bond together, using an adhesive agent, carrying out adhesion processing of the single side | surface of an acrylic resin film, etc.

  In addition, when laminating an acrylic resin film on a three-dimensional base material, an insert molding method in which an acrylic resin film shaped in advance is inserted into a mold for injection molding, vacuum molding in a mold, and injection molding It can bond together by well-known shaping | molding methods, such as the in-mold molding method to carry out. Among these, in-mold molding is preferable. In the in-mold molding method, the acrylic resin film is molded into a three-dimensional shape by vacuum molding, and then the base resin is poured into the molded product by injection molding and integrated, and therefore the acrylic having an acrylic resin film on the surface layer Laminated molded articles can be easily obtained. In addition, since film formation and injection molding can be performed in one step, the processability and economy are excellent.

  As a heating temperature in an in-mold molding method, it is more than the temperature which an acrylic resin film softens, and it is preferable that it is 70-170 degreeC normally. If it is less than 70 ° C., molding may be difficult, and if it exceeds 170 ° C., the surface appearance may be deteriorated or the releasability may be deteriorated.

  Such an acrylic resin molded product is excellent in appearance, weather resistance, transparency, printability, water whitening resistance, etc., particularly, protective films for outdoor building materials such as members surrounding water in bathrooms, kitchens, siding materials, etc. As it is very useful, it has high industrial value. Moreover, the acrylic resin molded object can be used also for uses other than the protective film of exterior building materials parts, such as water periphery members and outer wall materials, such as a bathroom and a kitchen, and a siding material. In particular, an acrylic resin film having a good appearance is, for example, a polarizing film protective film used for a polarizing plate of a liquid crystal display or the like, or a retardation film used for viewing angle compensation or retardation plate for retardation compensation It can also be used.

  Moreover, as an industrial application field of the laminated body which laminated | stacked the acrylic resin film, the high-intensity reflection material used for the safety sign aiming at a road sign, a display board, or visibility is mentioned, for example. Types of high-intensity reflectors include capsule-type reflectors in which aluminum-deposited glass beads are embedded in a substrate, and prism-type reflectors in which a prismatic resin sheet is used as a reflector. Also, the above-mentioned acrylic resin film can be suitably used as a protective film to be laminated on the surface of a reflective material. That is, since the high brightness reflector having the above-mentioned acrylic resin film on the surface has little decrease in the visibility of the high brightness reflector due to whitening such as rain water, the industrial use value is extremely high as a protective film of the high brightness reflector. .

  Hereinafter, the present invention will be further described by way of examples and comparative examples. In the following description, “parts” means “parts by mass”, and abbreviations / abbreviations mean compound names described in Table 1.

  First, evaluation methods and preparation examples of rubber-containing polymers will be described.

<Evaluation method>
(Melt viscosity)
The melt viscosity at a temperature of 240 ° C. and a shear rate of 96 (1 / sec), which were calculated by the Bargley correction and the Rabinovic correction, was measured using a twin capillary type rheometer (manufactured by Rosand, RH 7).
(MFR)
The discharge amount per unit time was measured at a temperature of 230 ° C. and a load of 10 kgf using a melt indexer (L243, manufactured by Techno-Seven Corporation) to calculate an MFR value of g / 10 min.
(Resin substitution)
The molten resin from the extruder outlet was visually observed, and the switching from the black resin to the transparent resin was evaluated based on the following criteria.
○: Black derived from carbon black does not remain in the molten resin until the end.
X: Black color derived from carbon black remains in the molten resin until the end.
(Cleanability)
The twin-screw extruder and the single-screw extruder were disassembled, and the inside of the cylinder and the die wall were observed and judged based on the following criteria.
○: Black derived from carbon black is not left on the wall.
X: Black color derived from carbon black remains on the wall surface.
(Transmittance)
The film obtained with a thickness of 300 μm was measured with a spectrophotometer, and the transmittance at a wavelength of 600 nm was measured. The transmittances at 1 kg discharge time and 3 kg discharge time from the start of film formation are shown in Table 4.

Preparation Example 1 Preparation of Rubber-Containing Multi -Stage Polymer (I) In a vessel equipped with a stirrer, 10.8 parts of deionized water was charged, and then 0.3 parts of MMA, 4.5 parts of n-BA, 0.2 parts of BDMA A monomer component (i-a-1) consisting of 0.05 parts of AMA and 0.025 parts of CHP was added and stirred and mixed at room temperature. Then, while stirring, 1.3 parts of surfactant A was charged into the above container, and stirring was continued for 20 minutes to prepare "Emulsified liquid 1".

  Next, 156.0 parts of deionized water was charged into a polymerization container equipped with a reflux condenser, and the temperature was raised to 74.degree. Furthermore, a mixture of 0.20 parts of sodium formaldehyde sulfoxylate, 0.0001 parts of ferrous sulfate and 0.0003 parts of EDTA in 4.5 parts of deionized water is prepared, and this mixture is added to the polymerization vessel. It was thrown in. Next, the emulsion 1 was dropped into the polymerization container over 9 minutes while stirring under a nitrogen atmosphere, and then the reaction was continued for 15 minutes to complete the polymerization of the polymer (I-a1).

Subsequently, a monomer component (i-a-2) consisting of 9.6 parts of MMA, 14.4 parts of n-BA, 1 part of BDMA, 0.25 parts of AMA and 0.016 parts of CHP is added to the polymerization vessel for 90 minutes. After the dropwise addition, the reaction was continued for 60 minutes to form a polymer (I-a2). Thus, a polymer (IA) containing the polymer (I-a1) and the polymer (I-a2) was obtained. When the respective monomer components for the polymer (I-a1) and the polymer (I-a2) are separately polymerized under the same conditions as described above, the Tg of the polymer (I-a1) is The Tg of the polymer (I-a2) at -48 ° C was -10 ° C.
Subsequently, a monomer component (ic) consisting of 6 parts of MMA, 4 parts of MA, 0.075 parts of AMA and 0.013 parts of CHP is dropped into the polymerization vessel over 45 minutes, and then the reaction is continued for 60 minutes, The polymer (I-C) was formed. When the monomer component for the polymer (I-C) was separately polymerized under the same conditions as described above, the Tg of the polymer (I-C) was 60.degree.

  Subsequently, a monomer component (i-b) consisting of 57 parts of MMA, 3 parts of MA, 0.075 parts of t-BHP and 0.248 parts of n-OM is dropped into the polymerization vessel over 140 minutes, and then the reaction is carried out for 60 minutes. The polymerization was continued to form a polymer (I-B), which was used as a polymer latex of the rubber-containing multistage polymer (I).

  The polymer latex of the obtained rubber-containing multistage polymer (I) is filtered using a vibrating filtration device in which a mesh (average opening: 54 μm) made of SUS is attached to a filter medium, and then 3.5 parts of calcium acetate The reaction product was salted out in an aqueous solution containing the compound, washed with water and recovered, and then dried to obtain a powdery rubber-containing multistage polymer (I). Table 2 shows a list of each monomer component.

Preparation Example 2 Production of Rubber-Containing Multistage Polymer (II) 186.3 parts of deionized water was charged into a polymerization container equipped with a reflux condenser, and the temperature was raised to 79 ° C. Furthermore, a mixture of 0.25 part of sodium formaldehyde sulfoxylate, 0.000025 part of ferrous sulfate and 0.000075 part of EDTA in 3.4 parts of deionized water is prepared, and this mixture is added to the polymerization vessel. It was thrown in.

  Then, while stirring under a nitrogen atmosphere, a monomer component comprising 11.25 parts of MMA, 12.5 parts of n-BA, 1.25 parts of St, 0.74 parts of BDMA, 0.09 parts of AMA and 0.044 parts of t-BHP A 1/10 charge of a mixture of ii-a-1) and 0.75 parts of surfactant A is dropped into the polymerization vessel over 4 minutes, and then the reaction is continued for 15 minutes, and then the remaining 9 / of the mixture is removed. After dropping 10 charges into the polymerization vessel over 108 minutes, 0.125 parts of sodium formaldehyde sulfoxylate is added at the reaction time for 40 minutes, and the reaction is continued for 55 minutes to polymerize the polymer (II-a1) Completed.

  Subsequently, a monomer component (ii-a-2) consisting of 30.94 parts of n-BA, 6.56 parts of St, 0.10 parts of BDMA, 0.65 parts of AMA and 0.106 parts of CHP was added to the above polymerization vessel for 180 minutes. After dropping into the inside, 0.125 parts of sodium formaldehyde sulfoxylate was added at the reaction time for 105 minutes, and the reaction was continued for 120 minutes to generate a polymer (II-a2). Thus, a polymer (II-A) containing the polymer (II-a1) and the polymer (II-a2) was obtained.

  Subsequently, a monomer component (ii-b) consisting of 35.63 parts of MMA, 1.88 parts of MA, 0.064 parts of t-BHP and 0.103 parts of n-OM is dropped into the polymerization vessel over 120 minutes, The combined (II-B) was formed and used as a polymer latex of the rubber-containing multistage polymer (II).

  The obtained polymer latex of the rubber-containing multistage polymer (II) is filtered using a vibrating filtration device in which a mesh (average mesh size: 54 μm) made of SUS is attached to a filter medium, and then 5.0 parts of calcium acetate The reaction product was salted out in an aqueous solution containing the compound, washed with water and recovered, and then dried to obtain a powdery rubber-containing multistage polymer (II). Table 2 shows a list of each monomer component.

Example 1
75 parts of rubber-containing multistage polymer (I) obtained in Preparation Example 1 as thermoplastic resin composition 1 (black resin) shown in Table 3; "Acrypet VH" manufactured by Mitsubishi Rayon Co., Ltd. as a thermoplastic polymer In 25 parts, as a compounding agent, 1.4 parts of "TINUVIN 234" manufactured by BASF, "Adekastab LA-57G" manufactured by ADEKA Co., Ltd. 0.3 parts, 0.1 part of BASF "IRGANOX 1076", carbon black After adding 2 parts, they are mixed using a Henschel mixer, and the obtained mixture is subjected to a cylinder temperature and a die temperature of 240 ° C. (extrusion conditions) using a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) The resin temperature T1 was 247 ° C. after setting 3) and extruding 3 kg. Subsequently, after setting the cylinder temperature and die | dye temperature of a twin-screw extruder to 280 degreeC, temperature rising for 1 hour was performed. Subsequently, the thermoplastic resin composition 2 (transparent resin) shown in Table 3 is mixed using a Henschel mixer, and the obtained mixture is extruded under an extrusion condition 2 shown in Table 4 to extrude 10.4 kg, and from the extrusion start A strand of φ3 mm was obtained, and the resin temperature T2 was 278 ° C. After extruding the thermoplastic resin composition 2 (transparent resin), the twin-screw extruder was disassembled, and the inside of the cylinder and the wall of the die were observed.

  Table 4 shows the results of evaluating the extrusion conditions, the resin substitution property and the washing property.

Comparative Example 1
Thermoplastic resin composition 1 (black resin) shown in Table 3 is mixed using a Henschel mixer, and the obtained mixture is subjected to cylinder temperature using a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) The die temperature was set to 240 ° C. (extrusion condition 1) and 3 kg was extruded. The resin temperature T1 was 249 ° C. Subsequently, after setting the cylinder temperature and die | dye temperature of a twin-screw extruder to 200 degreeC, temperature rising for 1 hour was performed. Subsequently, the thermoplastic resin composition 2 (transparent resin) shown in Table 3 is mixed using a Henschel mixer, and the obtained mixture is extruded under an extrusion condition 2 shown in Table 4 to extrude 11.0 kg, and from the extrusion start A strand of φ3 mm was obtained, and the resin temperature T2 was 226 ° C. After extruding the thermoplastic resin composition 2 (transparent resin), the twin-screw extruder was disassembled, and the inside of the cylinder and the wall of the die were observed. Table 4 shows the results of evaluating the resin substitution property and the washing property.

Example 2
As the thermoplastic resin composition 3 (black resin) shown in Table 3, 80 parts of the rubber-containing multistage polymer (I) obtained in Preparation Example 1 and the rubber-containing multistage polymer (II) 10 obtained in Preparation Example 2 As a thermoplastic polymer, 10 parts of "Acripet MD" manufactured by Mitsubishi Rayon Co., Ltd., 1.4 parts of "TINUBIN 234" manufactured by BASF as a compounding agent, "ADEKASTAB LA-57G" manufactured by ADEKA Co. Three parts, 0.1 part of BASF "IRGANOX 1076" and 2 parts of carbon black are added and mixed using a Henschel mixer, and the resulting mixture is dried, and then a single 150 mm wide T-die attached A resin temperature T1 of 241 ° C. was obtained by forming 3 kg of a film under the conditions shown in Table 4 with a shaft extruder (GM30 manufactured by GM Engineering). Subsequently, after setting the cylinder temperature and die | dye temperature of the single screw extruder with a T-die to 280 degreeC, temperature rising for 1 hour was performed. Subsequently, the thermoplastic resin composition 2 (transparent resin) shown in Table 3 is mixed using a Henschel mixer, and after the obtained mixture is dried, 7.3 kg is extruded under the conditions shown in Table 4 to obtain a thickness of 300 μm. The resin temperature T2 was 258 ° C. After extruding the thermoplastic resin composition 2 (transparent resin), the single-screw extruder with a T-die was disassembled, and the inside of the cylinder and the wall of the die were observed. Table 4 shows the results of evaluating the resin substitution property and the washing property.

Comparative Example 2
A thermoplastic resin composition 3 (black resin) shown in Table 3 is mixed using a Henschel mixer, and the resulting mixture is dried, and then a 150 mm wide single-screw extruder with T-die (Co. 3 kg of a film was formed by GM Engineering Ltd. GM 30) under the conditions shown in Table 4. The resin temperature T1 was 240 ° C. Subsequently, after setting the cylinder temperature and die | dye temperature of the single-screw extruder with a T-die to 230 degreeC, temperature rising for 1 hour was performed. Subsequently, the thermoplastic resin composition 2 (transparent resin) shown in Table 3 is mixed using a Henschel mixer, and after the obtained mixture is dried, 7.0 kg is extruded under the conditions shown in Table 4 to have a thickness of 300 μm. The resin temperature T2 was 221 ° C. After extruding the thermoplastic resin composition 2 (transparent resin), the single-screw extruder with a T-die was disassembled, and the inside of the cylinder and the wall of the die were observed. Table 4 shows the results of evaluating the resin substitution property and the washing property.

  The followings became clear from the above-mentioned Example and comparative example. That is, in Example 1 and Example 2, the pellet and film obtained by discharging | emitting the black resin in an extruder in a short time were favorable, and the washability in an extruder was also high. On the other hand, in Comparative Example 1 and Comparative Example 2, it was difficult to discharge the black resin in the extruder, and the resin substitution property and the cleaning property were also poor. From this, it was found that the fact that T2 is higher than T1 is excellent in terms of the resin discharge from the extruder and the cleaning property in the extruder.

  The thermoplastic resin molded product obtained by the production method of the present invention is free from the mixing of the thermally deteriorated products generated during the production of the previous product or the previous product, and a thermoplastic resin molded product having a good appearance can be obtained. In particular, a film-like acrylic resin molded article is a molded article having a weather resistance and a good appearance without a fish eye having a design property, and is used, for example, for interior and exterior applications of buildings, reflectors and interior applications of vehicles. can do.

Claims (9)

A method of producing a thermoplastic resin molded product using an extruder, comprising:
The extruder is an extruder formed by discharging the molten material of the thermoplastic resin composition A at a resin temperature T1, and the thermoplastic resin composition A remains inside,
The way is
By supplying the thermoplastic resin composition B to the extruder, the molten resin of the thermoplastic resin composition A remaining in the extruder is discharged from the extruder at a resin temperature T 2 to obtain a thermoplastic resin composition. Characterized in that A is replaced with a thermoplastic resin composition B,
The thermoplastic resin composition A and the thermoplastic resin composition B differ in composition, and
T1 and T2, to satisfy the equation (1) below,
(1) T1 <T2
After substituting the thermoplastic resin composition A with the thermoplastic resin composition B, subsequently, the thermoplastic resin composition B is further supplied to the extruder, and the melt of the thermoplastic resin composition B is subjected to resin temperature Including discharging and molding from the extruder at T3 ',
T2 and T3 'satisfy | fill the relational expression of following (2) method.
(2) T2> T3 ' The method according to claim 1, wherein
After substituting the thermoplastic resin composition A with the thermoplastic resin composition B, subsequently, the thermoplastic resin composition C is further supplied to the extruder, and the thermoplastic resin composition B remaining in the extruder Further replacing the thermoplastic resin composition B with the thermoplastic resin composition C by discharging the molten material from the extruder at a resin temperature T3;
Further supplying the thermoplastic resin composition C to the extruder, and discharging the molten product of the thermoplastic resin composition C from the extruder at a resin temperature T4 for forming;
The thermoplastic resin composition B and the thermoplastic resin composition C differ in composition, and
T3 and T4 satisfy | fill the relational expression of following (3) method.
(3) T3> T4 A method of producing a thermoplastic resin molded product using an extruder, comprising:
Supplying the thermoplastic resin composition A to the extruder, discharging the molten product of the thermoplastic resin composition A from the extruder at a resin temperature T1, and forming the thermoplastic resin molded body;
Discharging the melt of the thermoplastic resin composition A remaining in the extruder from the extruder at a resin temperature T2 by supplying the thermoplastic resin composition B to the extruder;
The thermoplastic resin composition B is further supplied to the extruder, and the melt of the thermoplastic resin composition B is discharged from the extruder at a resin temperature T3 ′ and molded to obtain a further thermoplastic resin molded body When,
Including
The thermoplastic resin composition A and the thermoplastic resin composition B differ in composition, and
A method wherein T1, T2 and T3 'satisfy the following equations (1) and (2).
(1) T1 <T2
(2) T2> T3 ' A method of producing a thermoplastic resin molded product using an extruder, comprising:
Supplying the thermoplastic resin composition A to the extruder, discharging the molten product of the thermoplastic resin composition A from the extruder at a resin temperature T1, and forming the thermoplastic resin molded body;
Discharging the melt of the thermoplastic resin composition A remaining in the extruder from the extruder at a resin temperature T2 by supplying the thermoplastic resin composition B to the extruder, and a thermoplastic resin composition C is further supplied to the extruder, and the molten resin of the thermoplastic resin composition B is discharged from the extruder at a resin temperature T3 to further replace the thermoplastic resin composition B with the thermoplastic resin composition C. And
The thermoplastic resin composition C is further supplied to the extruder, and the melt of the thermoplastic resin composition C is discharged from the extruder at a resin temperature T4 and molded to obtain a further thermoplastic resin molded body ,
Including
The thermoplastic resin composition A, the thermoplastic resin composition B and the thermoplastic resin composition C differ in composition, and
T1, T2, T3 and T4 satisfy all the relations below.
(1) T1 <T2
(3) T3> T4 At a temperature 240 ° C. conditions, the melt viscosity difference between the thermoplastic resin composition A and the thermoplastic resin composition B at a shear rate of 96 (1 / sec) is less than or equal to 500 Pa · s, of claims 1 to 4 The manufacturing method of the thermoplastic resin molded object as described in any one. At a temperature 240 ° C. conditions, the melt viscosity difference between the thermoplastic resin composition B and the thermoplastic resin composition C at a shear rate of 96 (1 / sec) is less than or equal to 500 Pa · s, in claim 2 or 4 The manufacturing method of the thermoplastic resin molding as described. The manufacturing method of the thermoplastic resin molded object as described in any one of Claims 1-6 whose thermoplastic resin molded object is a pellet or a film. The manufacturing method of the thermoplastic resin molded object as described in any one of Claims 1-7 whose thermoplastic resin composition is an acrylic resin composition. The method for producing a thermoplastic resin molded article according to any one of claims 1 to 8 , wherein the thermoplastic resin composition is a thermoplastic resin composition containing a rubber-containing polymer.