JP2014084362A - Visor containing methacrylic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a visor containing a methacrylic resin, having high heat resistance, and excellent in transparency, moist heat resistance, heat stability and molding processability.SOLUTION: A visor contains a methacrylic ester monomer unit (A): 50 to 97 mass%, a structure unit having at least one kind of ring structures selected from a group consisting of a maleimide based structure unit, a glutaric acid anhydride structure unit and a lactone ring structure unit in a main strain (B): 3 to 30 mass%, and another vinyl based monomer unit which can be polymerized to a methacrylic ester monomer (C): 0 to 20 mass%, and a methacrylic resin having a weight average molecular weight measured by gel permeation chromatography (GPC) of 65,000 to 300,000 (I).

Description

  The present invention relates to a visor containing a methacrylic resin.

Methacrylic resins represented by polymethyl methacrylate (PMMA) are widely used in the fields of optical materials, vehicle members, building materials, lenses, household goods, OA equipment, lighting equipment, etc. due to their high transparency. Yes.
In particular, in the field of vehicle parts, methacrylic resins are often used from the viewpoint of scratch resistance and transparency.

In recent years, various vehicle parts mounted on vehicles have been required to be thin in the form of molded pieces for weight reduction, but conventional methacrylic resins have insufficient heat resistance and have a certain thickness. Since there is a possibility of distortion when exposed to high temperature conditions, higher heat resistance is required than conventional methacrylic resins.
Especially in vehicle visor applications, impact may be applied outside the vehicle, so the rubber component may be mixed to impart impact resistance, but when the rubber component is mixed, the heat resistance usually decreases. . Therefore, high heat resistance is required for the methacrylic resin as the base resin.

In view of the above-described conventional circumstances, from the viewpoint of heat resistance, a polycarbonate resin may be used as the material of the visor. However, since the polycarbonate resin is inferior in scratch resistance and weather resistance, scratch resistance, weather resistance It is necessary to apply a hard coat to the surface for the application, and this causes a problem that the shape is limited and the cost is increased.
Conventionally, a sun visor for vehicles has been proposed in which an acrylic resin is coated with a surface layer containing an optical semiconductor for the purpose of shielding ultraviolet rays. (For example, refer to Patent Document 1).

JP-A-11-42939

  However, the acrylic resin described in Patent Document 1 has insufficient heat resistance as a visor material placed under high temperature conditions as described above, and silver may be generated during high temperature molding. Due to certain problems, higher heat resistance is required.

  Therefore, in the present invention, an object is to provide a visor containing a methacrylic resin, which is further improved in heat resistance and is excellent in transparency, moist heat resistance, thermal stability, and moldability. And

As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have completed the present invention.
That is, the present invention is as follows.

[1]
Methacrylic acid ester monomer unit (A): 50 to 97% by mass;
At least one structural unit (B) selected from the group consisting of a maleimide structural unit, a glutaric anhydride structural unit, a glutarimide structural unit, and a lactone ring structural unit (B) having a ring structure in the main chain: 3 to 30 masses %When,
0-20% by mass of other vinyl monomer units (C) copolymerizable with the methacrylic acid ester monomer,
Containing,
A visor containing a methacrylic resin (I) having a weight average molecular weight of 650,000 to 300,000 as measured by gel permeation chromatography (GPC).
[2]
10 to 99% by mass of the methacrylic resin (I),
Methacrylic resin (II) containing at least 80 to 99.5% by mass of a methacrylic acid ester monomer unit (A ′) and having a weight average molecular weight of 20,000 to 300,000 as measured by gel permeation chromatography (GPC) 90-1% by mass,
The visor according to [1], further including:
[3]
The visor according to [2] above, wherein the methacrylic resin obtained by mixing the methacrylic resin (I) and the methacrylic resin (II) has a weight average molecular weight of 650,000 to 300,000.
[4]
The rubber polymer (III) is further contained in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the resin component containing the methacrylic resin (I), according to any one of [1] to [3] visor.
[5]
The structural unit (B) having a ring structure in the main chain,
The visor according to any one of [1] to [4], including at least one structural unit selected from the group consisting of a glutarimide structural unit, a lactone ring structural unit, and a maleimide structural unit.
[6]
The visor according to any one of [1] to [5], wherein the structural unit (B) having a ring structure in the main chain includes a maleimide-based structural unit.
[7]
The structural unit (B) having a ring structure in the main chain,
The visor according to any one of [1] to [6], including an N-cyclohexylmaleimide structural unit and / or an N-aryl group-substituted maleimide structural unit.
[8]
The visor according to any one of [1] to [7], wherein the structural unit (B) having a ring structure in the main chain includes an N-aryl group-substituted maleimide structural unit.
[9]
The visor according to any one of [1] to [8], further including 0 to 5 parts by mass of a heat stabilizer with respect to 100 parts by mass of the methacrylic resin.
[10]
The visor according to [9], wherein the content Y (parts by mass) of the heat stabilizer satisfies the following formula (i) with respect to 100 parts by mass of the methacrylic resin.
(Y) ≧ 0.053 × [methacrylic acid ester monomer unit content / (B) content] −0.4 (i)
[11]
The visor according to [9] or [10], wherein the heat stabilizer is at least one selected from the group consisting of a hindered phenol-based antioxidant and a phosphorus-based antioxidant.
[12]
The other vinyl monomer unit (C) copolymerizable with the methacrylic acid ester monomer is composed of an acrylate monomer, an aromatic vinyl monomer, and a vinyl cyanide monomer. The visor according to any one of [1] to [11], which is formed of at least one selected from the above.
[13]
Other vinyl monomer units (C) copolymerizable with the methacrylic acid ester monomer are formed of at least one selected from the group consisting of methyl acrylate, ethyl acrylate, styrene, and acrylonitrile. The visor according to any one of [1] to [12].
[14]
Visor as described in any one of said [1] thru | or [13] whose Vicat softening temperature is 110 degreeC or more.
[15]
The visor according to any one of [1] to [14], wherein the thickness is 0.1 to 5 mm.

  ADVANTAGE OF THE INVENTION According to this invention, the visor containing methacrylic resin which is high in heat resistance, and is excellent also in transparency, wet heat resistance, thermal stability, and moldability can be provided.

Hereinafter, although the form for implementing this invention (henceforth "this embodiment") is demonstrated in detail, this invention is not limited to the following description, In the range of the summary Various modifications can be made.
Hereinafter, the structural unit constituting the polymer is referred to as “˜monomer unit”.
Moreover, when describing as a constituent material of the methacrylic resin which comprises the visor of this embodiment, a "unit" may be abbreviate | omitted and may only be described as "-monomer."

〔visor〕
The visor of this embodiment is
Methacrylic acid ester monomer unit (A): 50 to 97% by mass;
At least one structural unit (B) selected from the group consisting of a maleimide structural unit, a glutaric anhydride structural unit, a glutarimide structural unit, and a lactone ring structural unit (B) having a ring structure in the main chain: 3 to 30 masses %When,
0-20% by mass of other vinyl monomer units (C) copolymerizable with the methacrylic acid ester monomer,
A methacrylic resin (I) having a weight average molecular weight of 650,000 to 300,000 as measured by gel permeation chromatography (GPC).

The visor of this embodiment is
For 10 to 99 parts by mass of the methacrylic resin (I),
Methacrylic resin (II) containing at least 80 to 99.5% by mass of a methacrylic acid ester monomer unit (A ′) and having a weight average molecular weight of 20,000 to 300,000 as measured by gel permeation chromatography (GPC) 90 to 1 part by mass, may further be included.
The methacrylic resin (II) will be described later.

  In the present specification, the “visor” is a member having a function such as a horizontally long rain guard attached to the upper part of a side window of an automobile, and is not limited to the following, but for example, a side window visor, a weather A guard etc. are mentioned.

Hereinafter, the methacrylic resin contained in the visor of this embodiment will be described in detail.
(Methacrylic resin (I))
The methacrylic resin (I) is
Methacrylic acid ester monomer unit (A): 50 to 97% by mass;
At least one structural unit (B) selected from the group consisting of a maleimide structural unit, a glutaric anhydride structural unit, a glutarimide structural unit, and a lactone ring structural unit (B): 3 to 30 Mass%,
0-20% by mass of other vinyl monomer units (C) copolymerizable with the methacrylic acid ester monomer (A),
The weight average molecular weight measured by gel permeation chromatography (GPC) is 650,000 to 300,000.

The methacrylic resin (I) for the visor of this embodiment, and the mixed methacrylic resin in which the methacrylic resin (II) described later is further mixed with the methacrylic resin (I) as necessary are thin-walled molded products. High heat resistance is required because it is used in fields where conversion is required. From this viewpoint, the VICAT softening temperature of the molded body is preferably 110 ° C. or higher, more preferably 112 ° C. or higher, still more preferably 113 ° C. or higher, even more preferably 115 ° C. or higher, and even more preferably 117 ° C. or higher. Especially preferably, it is 120 ° C. or higher.
The VICAT softening temperature can be measured according to ISO 306 B50, and specifically, can be measured by the method described in Examples described later.
Hereinafter, it describes in detail about each monomer component of methacrylic resin (I).

<Methacrylic acid ester monomer unit (A)>
The methacrylic acid ester monomer unit (A) constituting the methacrylic resin (I) for the visor of the present embodiment (hereinafter sometimes referred to as the component (A)) may be represented by the following general formula (1). A monomer represented by is preferably used.

In the general formula (1), R ₁ represents a methyl group.
R ₂ represents a group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and may have a hydroxyl group on the carbon.
The methacrylic acid ester monomer represented by the general formula (1) is not particularly limited, and examples thereof include butyl methacrylate, ethyl methacrylate, methyl methacrylate, propyl methacrylate, isopropyl methacrylate, and methacrylic acid. Examples include cyclohexyl, phenyl methacrylate, methacrylic acid (2-ethylhexyl), methacrylic acid (t-butylcyclohexyl), benzyl methacrylate, and methacrylic acid (2,2,2-trifluoroethyl). From the viewpoint of optical properties, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and benzyl methacrylate are preferred. Methyl methacrylate is preferable from the viewpoint of availability.
The said methacrylic acid ester monomer may be used individually by 1 type, and may use 2 or more types together.

The methacrylic ester monomer unit (A) of the methacrylic resin (I) is contained in the methacrylic resin (I) from the viewpoint of heat resistance imparting effect by the structural unit (B) having a ring structure in the main chain described later. 50 to 97% by mass, preferably 55 to 97% by mass, more preferably 55 to 95% by mass, still more preferably 60 to 93% by mass, and even more preferably 60 to 90% by mass. .
In addition, also when the visor of this embodiment contains both the said methacrylic resin (I) and the methacrylic resin (II) mentioned later, the total amount of the methacrylic ester monomer unit contained in the said mixed methacrylic resin ((A) + (A ′)) is contained in the mixed methacrylic resin in an amount of 50 to 97% by mass from the viewpoint of imparting heat resistance by the structural unit (B) having a ring structure in the main chain described later. , Preferably 55 to 97% by mass, more preferably 55 to 95% by mass, still more preferably 60 to 93% by mass, and even more preferably 60 to 90% by mass.

<Structural unit (B) having a ring structure in the main chain>
The structural unit (B) having a ring structure in the main chain (hereinafter sometimes referred to as component (B)) constituting the methacrylic resin (I) for the visor of this embodiment is a maleimide structural unit. And at least one selected from the group consisting of a glutaric anhydride structural unit, a glutarimide structural unit, and a lactone ring structural unit.
The structural unit (B) having a ring structure in the main chain may be used alone or in combination of two or more structural units, and two or more monomer units in a common structural unit may be combined. You may use together.

[Maleimide structural unit (B-1)]
As the maleimide structural unit (B-1) constituting the methacrylic resin (I) for the visor of the present embodiment, a monomer represented by the following general formula (2) is preferably used.

R ₃ in the general formula (2) is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Which may have a substituent on the carbon atom.

The monomer for forming the maleimide-based structural unit (B-1) is not particularly limited. For example, maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N- Phenylmaleimide, N-methylphenylmaleimide, N-ethylphenylmaleimide, N-butylphenylmaleimide, N-dimethylphenylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N- (o-chlorophenyl) maleimide, N- (M-chlorophenyl) maleimide, N- (p-chlorophenyl) maleimide and the like.
From the viewpoint of imparting heat resistance and heat and humidity resistance, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N- (o-chlorophenyl) maleimide, N- (m-chlorophenyl) maleimide, N- ( p-chlorophenyl) maleimide, and from the viewpoint of easy availability and imparting heat resistance, more preferred are N-cyclohexylmaleimide and N-phenylmaleimide, and more preferred is N-phenylmaleimide.
The maleimide structural unit (B-1) described above may be used alone or in combination of two or more.

[Glutaric anhydride structural unit (B-2)]
Among the components (B) constituting the methacrylic resin (I) for the visor of the present embodiment, as a monomer for forming the glutaric anhydride structural unit (B-2), the following general formula (3) ) Is preferably used.

Here, in the general formula (3), R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the alkyl group is substituted with a hydroxyl group, for example. May be.

  Although it does not specifically limit about the manufacturing method of a glutaric anhydride structural unit (B-2), For example, the monomer of the structure represented by following General formula (4) is the above-mentioned methacrylic ester single monomer After copolymerization with the body (A), the glutaric anhydride structural unit can be introduced into the polymer by cyclization by heat treatment in the presence / absence of a catalyst.

Here, in the general formula (4), R ₅ is a hydrogen atom or a carbon atoms represent a 1-6 substituted or unsubstituted alkyl group, the alkyl group, for example, may have a hydroxyl group.
Moreover, as long as the effect of this invention can be exhibited, the structural unit represented by General formula (4) may remain unreacted in methacrylic resin (I).

[Glutarimide structural unit (B-3)]
Among the components (B) constituting the methacrylic resin (I) for the visor of the present embodiment, as a monomer for forming the glutarimide-based structural unit (B-3), the following general formula (5) A monomer represented by is preferably used.

Here, in the general formula (5), R ₂₁ and R ₂₂ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
The alkyl group may be substituted with, for example, a hydroxyl group.
R ₂₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.

The glutarimide-based structural unit (B-3) is obtained by copolymerizing the methacrylic acid ester monomer and / or methacrylic acid and then reacting with ammonia, amine, urea or unsubstituted urea at a high temperature, It can be obtained by a known method such as a method of reacting an acid anhydride with ammonia or an amine.
A preferable preparation method includes a method described in US Pat. No. 4,246,374 of RM Kopchik.

[Lactone ring structural unit (B-4)]
Among the components (B) constituting the methacrylic resin (I) for the visor of this embodiment, the monomer for forming the lactone ring structural unit (B-4) is represented by the following general formula (6). The monomers shown are preferably used.

In the formula _{(6), R 31, R} 32, R 33 represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms independently. The organic residue may contain an oxygen atom.
A lactone ring structural unit (B-4) may be used individually by 1 type, and may be used in combination of 2 or more type.
The method for producing the lactone ring-containing polymer is not particularly limited. For example, after polymerizing a polymer having a hydroxyl group and an ester group in the molecular chain, the obtained polymer is treated with the presence / absence of a predetermined catalyst. Examples thereof include a method of producing by introducing a lactone ring structure into a polymer by heat treatment in the presence.

The component (B) contained in the methacrylic resin (I) is preferably a glutarimide structural unit, a lactone ring structural unit, and a maleimide structural unit, more preferably from the viewpoint of thermal stability and moldability. Is a maleimide structural unit or glutarimide structural unit, more preferably a maleimide structural unit.
In view of availability, N-cyclohexylmaleimide-based structural units and / or N-aryl-substituted maleimide-based structural units are preferable, and N-aryl-substituted maleimide-based, considering the effect of imparting heat resistance with a small amount of addition. A structural unit is more preferable, and an N-phenylmaleimide-based structural unit is more preferable.

<Ratio of (B) component>
The structural unit (B) having a ring structure in the main chain has 3 to 3 in the methacrylic resin (I) from the viewpoint of imparting heat resistance and thermal stability and the strength and fluidity of the resulting methacrylic resin (I). 30% by mass is contained.
From the viewpoint of imparting heat resistance and thermal stability, it is preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 8% by mass or more.
In addition, from the viewpoint of maintaining the necessary strength and fluidity as a visor in a balanced manner, the structural unit (B) having a ring structure in the main chain is preferably 28% by mass or less in the methacrylic resin (I). Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 18 mass% or less, More preferably, it is less than 15 mass%.
Even in the case where both the visor of this embodiment, the methacrylic resin (I) and the methacrylic resin (II) described later are included, in the mixed methacrylic resin, a structural unit having a ring structure in the main chain ( From the viewpoint of imparting heat resistance and thermal stability, B) is contained in the mixed methacrylic resin in an amount of 3 to 30% by mass, preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 8% by mass. ing.

<Relationship between structural unit (B) having ring structure in main chain and thermal stability>
By including the structural unit (B) having a ring structure in the main chain in the methacrylic resin (I), when the methacrylic resin is placed in a high temperature environment, thermal decomposition is suppressed, and the amount of volatile components generated is reduced. It can be reduced. Thereby, the improvement effect of the thermal stability of the visor of this embodiment is acquired.

<Other vinyl monomer units (C) copolymerizable with methacrylate monomers>
In the methacrylic resin (I) for the visor of the present embodiment, the monomer constituting the component (A) (hereinafter simply simplified as the component (A) is described within a range not impairing the effects of the present invention. May contain other vinyl monomer units (C) that may be copolymerized (hereinafter may be referred to as component (C)).
The content in the case of using other vinyl monomer units (C) copolymerizable with the component (A) is methacrylic resin (I) from the viewpoint of exerting the heat resistance imparting effect by the component (B). ), 0 to 20% by mass, preferably 0 to 18% by mass, and more preferably 0 to 15% by mass.

  The monomer for forming the component (C) is not limited to the following, but for example, an aromatic vinyl monomer represented by the following general formula (7) and a general formula ( 8) Acrylic acid ester monomers represented by: vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Ester, ethylene glycol such as acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate or the like, and both terminal hydroxyl groups of its oligomer esterified with acrylic acid or methacrylic acid; neopentyl glycol di (meth) Two alcohols such as acrylate and di (meth) acrylate Those hydroxyl group esterified with acrylic acid or methacrylic acid; trimethylolpropane, those polyhydric alcohol derivatives such as pentaerythritol was esterified with acrylic acid or methacrylic acid; polyfunctional monomers such as divinylbenzene, and the like.

In the general formula (7), R ₄₄ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may have a hydroxyl group on the alkyl group.
n represents an integer of 0 to 5.
R ₄₅ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 8 carbon atoms, and an aryloxy group having 6 to 8 carbon atoms. And any one of R ₄₅ may be the same group or different groups.
Further, R ₄₅ may form a ring structure.

In the general formula (8), R ₆ is a hydrogen atom, and R ₇ is an alkyl group having 1 to 18 carbon atoms.

  As the component (C), materials can be appropriately selected according to the characteristics required for the visor of the present embodiment, but characteristics such as thermal stability, fluidity, mechanical characteristics, and chemical resistance are particularly necessary. In such a case, an aromatic vinyl monomer unit, an acrylate monomer unit, and a vinyl cyanide monomer unit are preferable.

[Aromatic vinyl monomer units (C-1)]
The monomer for forming the aromatic vinyl monomer unit is not particularly limited. For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, о-ethylstyrene, p-tert-butylstyrene, 1- Vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenyl benzene (α-methylstyrene), isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenyl Hexylbenzene, isopropyl Examples include phenyl octylbenzene.
These are appropriately selected according to required characteristics in the methacrylic resin for the visor of this embodiment. Among these, styrene and isopropenylbenzene are preferable, and styrene is more preferable from the viewpoint of imparting fluidity and reducing unreacted monomers by improving the polymerization conversion rate.

  The content in the case of using the aromatic vinyl monomer unit (C-1) is the sum of the components (A) and (B) in consideration of the balance between heat resistance, reduction of residual monomer species, and fluidity. When the amount is 100 parts by mass, it is preferably 23 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 18 parts by mass or less, still more preferably 15% by mass or less, and still more preferably 10 parts by mass. It is below mass%.

When the aromatic vinyl-based monomer unit (C-1) is used in combination with the maleimide monomer unit (B-1) described above, the blending ratio (mass ratio) is processed when the visor is molded. From the viewpoints of fluidity and the effect of reducing silver streaks due to residual monomer reduction, it is preferable to satisfy the following formula.
0.3 ≦ (C-1) / (B-1) ≦ 5
From the viewpoint of maintaining good color tone and heat resistance, the upper limit value is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less.
Moreover, it is preferable that it is 0.3 or more from a viewpoint of residual monomer reduction, More preferably, it is 0.4 or more.
The aromatic vinyl monomer (C-1) described above may be used alone or in combination of two or more.

[Acrylic acid ester monomer units (C-2)]
As a monomer for forming the acrylate ester monomer unit, as described above, in the general formula (8), a compound in which the substituent R ₇ is an alkyl group having 1 to 18 carbon atoms can be used. Among them, in the methacrylic resin for the visor of the present embodiment, methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid from the viewpoint of improving weather resistance, heat resistance, fluidity, and thermal stability. n-butyl, sec-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, and the like are preferable, and methyl acrylate, ethyl acrylate, and n-butyl acrylate are more easily available. From this viewpoint, methyl acrylate is more preferable.
In the case of using the acrylate monomer unit (C-2), the total amount of the component (A) and the component (B) is 100 parts by mass from the viewpoints of heat resistance and thermal stability. In this case, the amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less.
As the monomer for forming the acrylate monomer unit (C-2), only one type may be used alone, or two or more types may be used in combination.

[Vinyl cyanide monomer unit (C-3)]
The monomer for forming the vinyl cyanide monomer unit is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, vinylidene cyanide and the like. From the viewpoint of imparting chemical properties, acrylonitrile is preferably used.
In the case of using the vinyl cyanide monomer unit (C-3), the total amount of the component (A) and the component (B) is 100 parts by mass from the viewpoint of solvent resistance and heat resistance. When it is, it is preferable that it is 15 mass parts or less, More preferably, it is 12 mass parts or less, More preferably, it is 10 mass parts or less.

(Molecular weight and molecular weight distribution of methacrylic resin (I))
The methacrylic resin (I) for a visor of this embodiment has a weight average molecular weight of 650,000 or more and 300,000 or less. A methacrylic resin having a weight average molecular weight within this range is excellent in mechanical strength, solvent resistance and fluidity. Preferably it is 650,000 or more and 250,000 or less, More preferably, it is 70,000 or more and 230,000 or less.
The molecular weight distribution (weight average molecular weight / number average molecular weight: Mw / Mn) of the methacrylic resin (I) is 1.5 or more and 5 or less in consideration of the balance of fluidity, mechanical strength, and solvent resistance. Is preferred. More preferably, it is 1.5 or more and 4.5 or less, More preferably, it is 1.6 or more and 4 or less, More preferably, it is 1.6 or more and 3 or less, More preferably, it is 1.5 or more and 2.5 or less.
The weight average molecular weight and number average molecular weight of the methacrylic resin (I) for the visor of this embodiment can be measured by gel permeation chromatography (GPC).
That is, using a standard methacrylic resin, which is known in advance and has a monodispersed weight average molecular weight, number average molecular weight, and peak molecular weight, and an analytical gel column that elutes a high molecular weight component first, elution time and weight average molecular weight Create a calibration curve from Next, from the obtained calibration curve, the weight average molecular weight and the number average molecular weight of the sample of the methacrylic resin to be measured can be obtained.
Specifically, it can measure by the method as described in the Example mentioned later.

(Residual monomer amount)
In the visor of the present embodiment, the residual monomer is 0.1% by mass to 1.5% by mass in the visor of the present embodiment, considering the balance of heat resistance, fluidity, moldability during molding, and scratch resistance. It is preferable that More preferably 0.1% by mass to 1% by mass, further preferably 0.2% by mass to 1% by mass, even more preferably 0.2% by mass to 0.8% by mass, and still more preferably 0.3% by mass. % To 0.8% by mass.
The amount of residual monomer can be measured by gas chromatography, and specifically can be measured by the method described in the examples described later.
The residual monomer here means the monomer remaining in the resin, that is, the components (A), (B) and (C) contained in the methacrylic resin (I), and further a methacrylic resin (II) described later. ) Component (A ′) and other copolymerizable components (C ′) included in the above), which can be measured by gas chromatography.
In addition, when using a maleimide monomer as the component (B), from the viewpoint of color tone and fluidity, heat resistance, thermal stability and scratch resistance, the residual monomer content of the remaining maleimide monomer is It is preferable that it is 0.001 mass%-0.8 mass% in the visor of this embodiment. More preferably, it is 0.002 mass%-0.7 mass%, More preferably, it is 0.003 mass%-0.5 mass%, More preferably, it is 0.005 mass%-0.5 mass%, More preferably, It is 0.01 mass%-0.44 mass%.

(Method for producing methacrylic resin (I))
Hereinafter, although the manufacturing method of methacrylic resin (I) for the visor of this embodiment is demonstrated, it is not limited to the method shown below.
The methacrylic resin (I) can be copolymerized with the methacrylic acid ester monomer unit (A), the structural unit (B) having a ring structure in the main chain, and the methacrylic acid ester monomer as necessary. Such other monomers for forming the vinyl monomer unit (C) can be used to produce the polymer by bulk polymerization, solution polymerization, suspension polymerization, precipitation polymerization, or emulsion polymerization. A bulk polymerization method, a solution polymerization method and a suspension polymerization method are preferably used, a solution polymerization method and a suspension polymerization method are more preferable, and a suspension polymerization method is more preferably used.

<Production method by solution polymerization method>
When the methacrylic resin (I) is produced by the solution polymerization method, an organic solvent that is a good solvent for the methacrylic resin is used in consideration of the removal efficiency in the step of removing the monomer remaining in the methacrylic resin.
Considering the solubility of the copolymer constituting the methacrylic resin (I), the solubility parameter δ of the organic solvent is preferably 7.0 to 12.0 (cal / cm ³ ) ^1/2 , More preferably, it is 8.0-11.0, More preferably, it is 8.2-10.5.
The value of the solubility parameter δ and how to obtain the value are described in, for example, K. P. P-P118 in Non-Patent Document “Journal of Paint Technology Vol. 42, No. 541, February 1970”. L. Hoy “New Values of the Solubility Parameters From Vapor Pressure Data” For example, Brandrup et al., “Polymer Handbook Fourth Edition” P-VII / 675-P714 can be referred to.
1 (cal / cm ³ ) ^1/2 is about 0.489 (MPa) ^1/2 .

The addition amount of the organic solvent used in the polymerization step of the methacrylic resin (I) for the visor of the present embodiment is an amount that can be easily removed without the occurrence of precipitation of the copolymer or the used monomer during the production. It is preferable that
When the solution polymerization method is used, the amount of the organic solvent is preferably 10 parts by mass or more and 200 parts by mass or less when the total amount of the monomers to be blended is 100 parts by mass. More preferably, they are 25 mass parts or more and 200 mass parts or less, More preferably, they are 50 mass parts or more and 200 mass parts or less, More preferably, they are 50 mass parts or more and 150 mass parts or less.

The polymerization temperature in the case of producing the methacrylic resin (I) by solution polymerization may be any temperature at which polymerization proceeds, but is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 80 ° C. from the viewpoint of productivity. It is at least 200 ° C. More preferably, it is 90 degreeC or more and 200 degrees C or less, More preferably, it is 100 degreeC or more and 180 degrees C or less, More preferably, it is 110 degrees C or more and 170 degrees C or less.
The polymerization time is not particularly defined as long as the required degree of polymerization can be obtained, but it is preferably 0.5 hours or more and 10 hours or less, more preferably 1 hour from the viewpoint of productivity and the like. More than 8 hours.
In the polymerization step of the methacrylic resin (I), the dissolved oxygen concentration in the polymerization solution is preferably 10 ppm or less. The dissolved oxygen concentration can be measured using, for example, a dissolved oxygen meter DO meter B-505 (manufactured by Iijima Electronics Co., Ltd.). As a method for lowering the dissolved oxygen concentration, a method of bubbling an inert gas in the polymerization solution, and an operation of releasing the pressure after pressurizing the container containing the polymerization solution with an inert gas to about 0.2 MPa before the polymerization are repeated. A method such as a method and a method of passing an inert gas in a container containing a polymerization solution can be appropriately selected.

<Production method by suspension polymerization method>
When the methacrylic resin (I) for the visor of this embodiment is produced by suspension polymerization such as organic suspension polymerization method or inorganic suspension polymerization method, a polymerization step and a washing step using a stirrer described later The particulate methacrylic resin (I) is produced through a dehydration step and a drying step. Usually, an aqueous suspension polymerization method using water as a medium is preferably used.
<Polymerization process>
Using a stirrer to be described later, a monomer, a suspending agent, and a polymerization initiator and other additives as necessary are appropriately fed into the stirrer to perform polymerization, and a methacrylic resin slurry is prepared. obtain.
The stirrer used in the polymerization process to obtain methacrylic resin by suspension polymerization method includes inclined paddle blade, flat paddle blade, propeller blade, anchor blade, fiddler blade (retracted blade), turbine blade, bull margin Stirring devices with stirring blades such as blades, Max blend blades, full zone blades, ribbon blades, supermix blades, intermig blades, special blades and axial flow blades, stirring devices with shovel blades inside, chopper blades inside Examples of the stirring device include known stirring devices such as a stirring device having a rotating disk such as a disk type, a notch disk type, or a screw type.
The stirring speed at the time of polymerization depends on the type of stirring device used, the stirring efficiency of the stirring blade, the capacity of the polymerization tank, etc., but it is possible to obtain an appropriate particle size, and a component having a particle size of less than 0.15 mm Considering that the amount can be reduced, polymerization stability and the like, it is preferably about 1 to 500 revolutions / minute.

In the polymerization step of the methacrylic resin (I), the temperature at which the raw material is added may be within a range where the effects of the present invention can be exerted, and is preferably 0 ° C. or higher and lower than the boiling point of the raw material to be used.
If the temperature is high, the raw material tends to volatilize at the time of addition, so the composition of the resulting copolymer may change. In addition, depending on the raw material used, there is a possibility that a part of the raw material is hydrolyzed by contact with water at a high temperature, and the color tone may be greatly changed under wet heat conditions. When the temperature is lower than 0 ° C., it takes time to increase the temperature after the addition of the raw material, and therefore it is preferable to add the raw material mixture at a certain temperature.
Specifically, it is preferably 0 ° C or higher and 85 ° C or lower, more preferably 10 ° C or higher and 85 ° C or lower, further preferably 10 ° C or higher and 80 ° C or lower, and even more preferably 15 ° C or higher and 70 ° C or lower, More preferably, it is 15 degreeC or more and 60 degrees C or less.

The temperature in the suspension polymerization step is preferably 40 ° C. or higher and 90 ° C. or lower in consideration of productivity and the amount of aggregates produced. More preferably, they are 50 degreeC or more and 85 degrees C or less, More preferably, they are 60 degreeC or more and 80 degrees C or less, More preferably, they are 65 degreeC or more and 80 degrees C or less.
In the case of producing by suspension polymerization, the polymerization time is preferably 20 minutes or more and 240 minutes or less from the viewpoint of effectively suppressing heat generation during polymerization and reducing the generation of aggregates to be described later and the reduction of residual monomer. is there. More preferably, they are 30 minutes or more and 210 minutes or less, More preferably, they are 45 minutes or more and 180 minutes or less, More preferably, they are 60 minutes or more and 180 minutes or less, More preferably, they are 90 minutes or more and 150 minutes or less.

Further, from the viewpoint of reducing the residual monomer, it is preferable to raise the temperature to a temperature higher than the polymerization temperature after the polymerization step and hold it for a certain time.
The temperature at the time of holding is preferably higher than the polymerization temperature from the viewpoint that the degree of polymerization can be increased, and is preferably raised by 5 ° C. or more from the polymerization temperature.
When raising temperature, it is preferable that it is below the glass transition temperature of methacrylic resin (I) obtained from a viewpoint which prevents aggregation of the polymer obtained. Specifically, it is 120 ° C. or lower, preferably 80 ° C. or higher and 120 ° C. or lower, more preferably 90 ° C. or higher and 120 ° C. or lower, even more preferably 93 ° C. or higher and 120 ° C. or lower, even more preferably 93 ° C. or higher and 110 ° C. or lower. It is.

By performing polymerization according to the polymerization temperature and holding time described above, polymer particles having a small angle of repose can be obtained after the drying step described below.
The time for maintaining the temperature after the temperature rise is preferably 15 minutes or more and 360 minutes or less, more preferably 30 minutes or more and 240 minutes or less, more preferably 30 minutes or more and 180 minutes, in view of the effect of reducing the residual monomer. Hereinafter, it is more preferably 30 minutes or longer and 150 minutes or shorter, and even more preferably 30 minutes or longer and 120 minutes or shorter.

<Washing process>
The slurry of the methacrylic resin (I) obtained through the above-described polymerization step is preferably subjected to a washing step such as acid washing, water washing, and alkali washing in order to remove the suspending agent.
In these washing steps, the number of times of washing operation may be selected from the work efficiency and the suspension removal efficiency, and may be repeated once or multiple times.
What is necessary is just to select the temperature at the time of performing washing | cleaning operation in consideration of the removal efficiency of a suspension agent, the coloring degree of the copolymer obtained, etc., and it is preferable that it is 20-100 degreeC. More preferably, it is 30-95 degreeC, More preferably, it is 40-95 degreeC.

  In addition, the cleaning time per cleaning operation is preferably 10 to 180 minutes, more preferably 20 to 150 minutes, from the viewpoints of cleaning efficiency, repose angle reduction effect, and process simplicity.

The pH of the cleaning solution used at the time of the cleaning may be within a range where the suspension can be removed, but is preferably pH 1-12.
The pH for acid washing is preferably pH 1-5, more preferably pH 1.2-4, from the viewpoint of the removal efficiency of the suspending agent and the color tone of the resulting copolymer. The acid used at that time is not particularly limited as long as the suspending agent can be removed, and conventionally known inorganic acids and organic acids can be used. As an example of the acid that is preferably used, the inorganic acid includes hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, boric acid and the like, and each may be used in a diluted solution diluted with water or the like. Examples of the organic acid include those having a carboxyl group, a sulfo group, a hydroxy group, a thiol group, or an enol. Considering the effect of removing the suspending agent and the color tone of the resulting resin, more preferred are nitric acid, sulfuric acid, and organic acids having a carboxyl group.
After the acid cleaning, it is preferable to further perform water washing or alkali washing from the viewpoint of reducing the color tone and angle of repose of the polymer obtained.
The alkaline solution used for the alkali cleaning is preferably pH 7.1 to 12, more preferably pH 7.5 to 11, and further preferably pH 7.5 to 10.5.
Although the alkaline component used for alkali washing is not limited to the following, for example, tetraalkylammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide and the like are preferably used. Alkali metal hydroxides and alkaline earth metal hydroxides are more preferable, and lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, hydroxide are more preferable. Calcium and barium hydroxide are more preferable, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide are more preferable, and sodium hydroxide and potassium hydroxide are still more preferable.
These alkaline components can be used by adjusting the pH by diluting with water or the like.

<Dehydration process>
As a method for separating the polymer particles from the polymer slurry of the obtained methacrylic resin, a conventionally known method can be applied.
For example, a dehydration method using a centrifuge that shakes off water using centrifugal force, a method of separating water by sucking and removing water on a porous belt or a filtration membrane, and the like can be mentioned.

<Drying process>
The water-containing methacrylic resin (I) obtained through the dehydration step described above can be recovered by performing a drying treatment by a known method.
For example, hot air drying for drying by sending hot air into the tank from a hot air blower or blow heater, etc., vacuum drying for drying by heating as necessary after reducing the pressure inside the system, and obtained polymer For example, barrel drying for removing moisture by rotating the container in a container, spin drying for drying using centrifugal force, and the like.
These methods may be used alone or in combination.

  The water content of the obtained methacrylic resin (I) is preferably 0.01% by mass to 1% by mass, more preferably, considering the handleability and color tone of the obtained methacrylic resin (I). It is 0.05 mass%-1 mass%, More preferably, it is 0.1 mass%-1 mass%, More preferably, it is 0.27 mass%-1 mass%. The water content of the resulting methacrylic resin (I) can be measured using the Karl Fischer method.

When the methacrylic resin (I) is produced by using the suspension polymerization method described above, the resulting methacrylic resin (I) is usually substantially spherical, but some aggregates may be formed.
The said aggregate refers to the residue which remains on a sieve, when the obtained polymer is passed through a 1.68 mm mesh sieve.
When the aggregate remains in the methacrylic resin (I), the color tone of the resulting methacrylic resin (I) tends to decrease. The amount of aggregates in the methacrylic resin (I) is preferably 1.2% by mass or less, more preferably 1.0% by mass or less.
The agglomerate content was determined by measuring the weight after passing through a sieve of 1.68 mm mesh and drying what was left on the sieve in a drying oven at 80 ° C. for 12 hours, and the obtained weight was the total amount of raw materials. It is obtained by dividing by the calculation of the aggregate production (mass%).

The average particle diameter of the methacrylic resin (I) obtained by using the above-described suspension polymerization method is preferably 0.1 mm or more in consideration of workability during molding and extrusion, etc. Is also more preferably from 0.1 mm to 1 mm, still more preferably from 0.1 mm to 0.5 mm, and even more preferably from 0.1 mm to 0.4 mm.
The average particle diameter can be measured, for example, based on JIS-Z8801, and sieves (JTS-200-45-44 (aperture 500 μm), 34 (aperture 425 μm), 35 (aperture 355 μm) manufactured by Tokyo Screen) , 36 (aperture 300 μm), 37 (aperture 250 μm), 38 (aperture 150 μm), 61 (a saucer)) using a screening tester TSK B-1 for 10 minutes with vibration force MAX It is possible to measure by measuring the weight of particles remaining on each sieve when performing the measurement and determining the particle diameter when the weight is 50%.

In various polymerization methods for producing the methacrylic resin (I) contained in the visor of the present embodiment, that is, in the polymerization step in the bulk polymerization method, the solution polymerization method, the suspension polymerization method, or the emulsion polymerization method, For the purpose of adjusting the degree of polymerization, a polymerization initiator may be used.
The polymerization initiator is not limited to the following when performing radical polymerization, but examples thereof include di-t-butyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide, and t-butyl peroxide. Oxyneodecanate, t-butylperoxypivalate, dilauroyl peroxide, dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3 , 3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and the like, azobisisobutyronitrile, azobisisovaleronitrile, 1,1-azobis (1- Cyclohexanecarbonitrile), 2,2'-azobis-4-methoxy-2,4-azo Azo-based general radical polymerization initiators such as sisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis-2-methylbutyronitrile and the like can be mentioned. .
These may be used alone or in combination of two or more.
A combination of these radical polymerization initiators and an appropriate reducing agent may be used as a redox initiator.
These polymerization initiators are generally used in the range of 0 to 1 part by mass with respect to 100 parts by mass of the total amount of all monomers used, taking into consideration the polymerization temperature and the half-life of the initiator. Can be selected as appropriate.

When selecting bulk polymerization method, cast polymerization method, suspension polymerization method, from the viewpoint of preventing coloring of methacrylic resin, peroxide initiators lauroyl peroxide, decanoyl peroxide, and t-butylperoxy- 2-ethylhexanoate and the like can be particularly preferably used, and lauroyl peroxide is particularly preferably used.
In addition, in the case of performing solution polymerization or bulk polymerization at a high temperature of 90 ° C. or higher, a peroxide, azobis initiator, etc. having a 10-hour half-life temperature of 80 ° C. or higher and soluble in the organic solvent to be used preferable. Such a polymerization initiator is not limited to the following, and examples thereof include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, cyclohexane peroxide, and 2,5-dimethyl. Examples include -2,5-di (benzoylperoxy) hexane, 1,1-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile and the like.
These polymerization initiators are preferably used in the range of 0 to 1 part by mass with respect to 100 parts by mass of the total amount of all monomers used.

In the production process of the methacrylic resin (I) contained in the visor of the present embodiment, the molecular weight of the polymer to be produced can be controlled within a range that does not impair the object of the present invention.
For example, the molecular weight can be controlled by using chain transfer agents such as alkyl mercaptans, dimethylacetamide, dimethylformamide, triethylamine, etc., dithiocarbamates, triphenylmethylazobenzene, iniferters such as tetraphenylethane derivatives, etc. Can control the molecular weight by adjusting the addition amount of these chain transfer agents and iniferters.
When these chain transfer agents and iniferters are used, alkyl mercaptans are preferably used from the viewpoint of handleability and stability, and are not limited to the following. For example, n-butyl mercaptan, n-octyl mercaptan are used. , N-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, 2-ethylhexyl thioglycolate, ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate) ) And the like.
These can be appropriately added according to the required molecular weight, but generally used in the range of 0.001 to 3 parts by mass with respect to 100 parts by mass of the total amount of all monomers used. .
Other molecular weight control methods include a method of changing the polymerization method, a method of adjusting the amount of the polymerization initiator, and a method of changing the polymerization temperature.
As these molecular weight control methods, only one type of method may be used alone, or two or more types may be used in combination.

(Methacrylic resin (II))
The visor of this embodiment further includes at least 80 to 99.5% by mass of a methacrylic acid ester monomer unit (A ′) in addition to the methacrylic resin (I) described above, and gel permeation chromatography (GPC). The methacrylic resin (II) having a weight average molecular weight measured in step 20,000 to 300,000 may be included.
In this case, from the balance of heat resistance and color tone, it is preferable to contain 90 to 1% by mass of methacrylic resin (II) with respect to 10 to 99% by mass of methacrylic resin (I), more preferably methacrylic resin. 15 to 95% by mass of (I), 85 to 5% by mass of methacrylic resin (II), more preferably 200 to 80% by mass of methacrylic resin (I), and 80 to 20 mass of methacrylic resin (II). %.

  When the methacrylic resin (I) for the visor of this embodiment is used in combination with a methacrylic resin (II) different from the methacrylic resin (I), methacrylic acid constituting the methacrylic resin (II) As the ester monomer unit (A ′), a monomer represented by the following general formula (9) is preferably used.

In the above formula, R ₅₁ represents a methyl group.
R ₅₂ represents a group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and may have a hydroxyl group on the carbon.
The methacrylic acid ester monomer (A ′) represented by the general formula (9) is not limited to the following. For example, butyl methacrylate, ethyl methacrylate, methyl methacrylate, propyl methacrylate, methacrylic acid Isopropyl, cyclohexyl methacrylate, phenyl methacrylate, methacrylic acid (2-ethylhexyl), methacrylic acid (t-butylcyclohexyl), cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid (2,2,2-trifluoro) Ethyl) and the like, and methyl methacrylate is preferred from the viewpoint of availability.
The said methacrylic acid ester monomer may be used individually by 1 type, and may use 2 or more types together.

  The methacrylic acid ester monomer unit (A ′) is preferably contained in the methacrylic resin (II) in an amount of 80 to 99.5% by mass in consideration of the balance of heat resistance, thermal stability and fluidity. Is 85 to 99.5% by mass, more preferably 90 to 99% by mass, still more preferably 92 to 99.3% by mass, still more preferably 92 to 99% by mass, and still more preferably 94 to 99% by mass. .

The methacrylic resin (II) includes the methacrylic acid ester monomer unit (A ′) and another vinyl monomer unit (C ′) copolymerizable with the (A ′).
The monomer used to form another vinyl monomer unit (C ′) copolymerizable with (A ′) contained in the methacrylic resin (II) is limited to the following. Although not a thing, For example, the acrylate monomer represented by following General formula (10);

(In General Formula (10), R ₆₃ is a hydrogen atom, and R ₆₄ is an alkyl group having 1 to 18 carbon atoms.), Α, β-unsaturated acids such as acrylic acid and methacrylic acid; acrylic acid , Β-unsaturated acids such as methacrylic acid; unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, itaconic acid, cinnamic acid and their alkyl esters; styrene, o-methylstyrene, m-methyl Styrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, о-ethylstyrene, Styrenic monomers such as p-tert-butylstyrene and isopropenyl benzene (α-methylstyrene); 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenyl Aromatic vinyl monomers such as ethylene, isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene; acrylonitrile, methacrylonitrile, etc. Vinyl cyanide monomers; N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; amides such as acrylamide and methacrylamide; ethylene glycol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate Esterylene glycol such as ethylene glycol or its both hydroxyl groups esterified with acrylic acid or methacrylic acid; the hydroxyl groups of two alcohols such as neopentyl glycol di (meth) acrylate and di (meth) acrylate are acrylic acid or methacrylic An esterified with an acid; a polyhydric alcohol derivative such as trimethylolpropane or pentaerythritol esterified with acrylic acid or methacrylic acid; a polyfunctional monomer such as divinylbenzene.
In particular, in the visor of this embodiment, from the viewpoint of improving weather resistance, heat resistance, fluidity, and thermal stability, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and sec- Butyl, 2-ethylhexyl acrylate and the like are preferable, more preferably methyl acrylate, ethyl acrylate and n-butyl acrylate, and methyl acrylate and ethyl acrylate are more preferable from the viewpoint of availability. .
The said vinyl-type monomer may be used individually by 1 type, and may use 2 or more types together.

  In the methacrylic resin (II), the amount of monomer added to form another vinyl monomer unit (C ′) copolymerizable with the methacrylic acid ester monomer unit (A ′) is Although it can be appropriately selected within a range that does not impair the properties of the resulting methacrylic resin (II), from the viewpoint of fluidity, heat resistance, and thermal stability, 100% by mass of all monomers constituting the methacrylic resin (II) Is 0.5 to 20% by mass, preferably 0.5 to 15% by mass, more preferably 0.5 to 10% by mass, still more preferably 0.7 to 8% by mass, Still more preferably, it is 1-8 mass%, More preferably, it is 1-6 mass%.

<Weight average molecular weight, number average molecular weight, etc. of methacrylic resin (II)>
The weight average molecular weight, number average molecular weight, and peak molecular weight of the methacrylic resin (II) can be measured by gel permeation chromatography (GPC).
Specifically, using a standard methacrylic resin, which is known in advance and has a monodispersed weight average molecular weight, number average molecular weight, and peak molecular weight, and an analytical gel column that elutes a high molecular weight component first, elution time and Create a calibration curve from the weight average molecular weight.
Next, from the obtained calibration curve, the weight average molecular weight, number average molecular weight, and peak molecular weight of the sample of the methacrylic resin to be measured can be obtained.
The weight average molecular weight of the methacrylic resin (II) may be appropriately selected so as to obtain desired heat resistance, fluidity, and thermal stability in consideration of the heat resistance, processing fluidity, and thermal stability of the methacrylic resin. However, the weight average molecular weight is preferably 20,000 to 300,000. More preferably, it is 20,000-250,000, More preferably, it is 50,000-250,000, Especially preferably, it is 70,000-230,000.
The molecular weight distribution (Mw / Mn) may be appropriately selected in consideration of the balance of properties such as fluidity and mechanical properties, but is preferably 1.5 to 7, more preferably 1.5 to 5, More preferably, it is 1.5-4.
In addition, the weight average molecular weight of the mixed methacrylic resin of the methacrylic resin (I) and the methacrylic resin (II) described above is 650,000 or more and 300,000 from the viewpoint of mechanical strength, solvent resistance and fluidity. Or less, more preferably 650,000 to 250,000, and even more preferably 70,000 to 230,000.

(Method for producing methacrylic resin (II))
The methacrylic resin (II) uses a methacrylic acid ester monomer (A ′) and another vinyl monomer (C ′) that can be copolymerized with the methacrylic acid ester monomer. It can be produced by a polymerization method, a suspension polymerization method, a precipitation polymerization method, or an emulsion polymerization method. A bulk polymerization method, a solution polymerization method and a suspension polymerization method are preferably used, a solution polymerization method and a suspension polymerization method are more preferable, and a suspension polymerization method is more preferably used.
As a specific method, a method similar to the method for producing the methacrylic resin (I) described above can be applied.

(Methacrylic resin composition)
<Rubber polymer (III)>
The visor of this embodiment includes the methacrylic resin (I) described above, methacrylic resin (II) as necessary, a rubbery polymer (III) described later, predetermined other resins, and predetermined additives. It can also be produced using a combined methacrylic resin composition.
In addition, the methacrylic resin included in the visor of the present embodiment may include a case of only the methacrylic resin (I) and a case of including the methacrylic resin (I) and the methacrylic resin (II). These may be collectively referred to simply as “methacrylic resin”.

  The rubbery polymer (III) is not particularly limited as long as the effects of the present invention can be exhibited, and known materials can be used. For example, rubber particles having a multilayer structure such as general butadiene-based ABS rubber, acrylic-based, polyolefin-based, silicone-based, and fluororubber can be used. When high transparency is required, the rubber polymer (III) having a refractive index close to that of the methacrylic resins (I) and (II) described above can be preferably used. It can be particularly preferably used.

  In the visor of the present embodiment, when the rubbery polymer (III) is contained, an optimum amount may be blended depending on required properties such as heat resistance retention, impact resistance imparting, and fluidity. It is preferable to set it as 1-100 mass parts with respect to 100 mass parts of resin components which match | combined the methacrylic-type resin component mentioned above and the other resin component added as needed, More preferably, it is 10-100 mass parts.

The rubbery polymer (III) suitably used in the present embodiment is not limited to the following, and examples thereof include the following acrylic rubbery polymers.
[Example 1: Rubber polymer disclosed in Japanese Patent Publication No. 60-17406]
The rubbery polymer of Example 1 is a multilayer structure particle produced by the following steps (A) to (C).
Step (A): Dispersion of a polymer mainly composed of methyl methacrylate by emulsion polymerization of methyl methacrylate alone or a mixture of methyl methacrylate and a monomer copolymerizable therewith, and having a glass transition point of 25 ° C. or higher. A first layer forming step.
Step (B): an alkyl acrylate that forms a copolymer having a glass transition point of 25 ° C. or lower when polymerized to the product obtained by the step (A), and a monomer copolymerizable therewith, or A second layer step in which a mixture containing a polyfunctional crosslinking agent and 0.1 to 5% by mass of a polyfunctional grafting agent based on the total weight of the mixture is added and subjected to emulsion polymerization.
Step (C): Concatenating methyl methacrylate or a monomer mixture mainly composed thereof, which forms a polymer having a glass transition point of 25 ° C. or higher when polymerized to the product obtained in the step (B). A third layer forming step of emulsion polymerization in multiple stages while increasing the transfer agent stepwise.
The multilayer structured particles are multilayer structured particles made of acrylic rubber in which the molecular weight of the third layer gradually decreases from the inside toward the outside.

[Example 2: Rubber polymer disclosed in JP-A-8-245854]
The rubbery polymer of Example 2 is the following acrylic multilayer structure polymer powder.
The acrylic multilayer structure polymer powder has a polymer melting start temperature of 235 ° C. or higher. The inner layer contains a polymer having a glass transition temperature Tg of 25 ° C. or lower when polymerized alone, and the inner layer is at least one soft polymer layer.
The outermost layer is a hard polymer layer containing a polymer having a Tg of 50 ° C. or higher when polymerized alone.
The rubber polymer of Example 2 is an acrylic multilayer structure polymer powder containing a coagulated powder obtained by coagulating an emulsion latex of an acrylic multilayer structure polymer, and is a fine powder having a particle size of 212 μm or less after drying. The void volume with a pore diameter of 5 μm or less measured by a mercury intrusion method of the solidified powder after drying is 0.7 cc or less per unit area.

[Example 3: Rubber polymer disclosed in JP-B-7-68318]
The rubbery polymer of Example 3 is a multilayer structure acrylic polymer having the following requirements (a) to (g).
That is, the multilayer structure acrylic polymer is
(A) 90 to 99% by mass of methyl methacrylate, 1 to 10% by mass of alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, and allyl, methallyl, or clothy of α, β-unsaturated carboxylic acid copolymerizable therewith. The innermost hard layer polymer 25-45 mass obtained by polymerizing a monomer mixture consisting of 0.01 to 0.3 mass% of a graft-bondable monomer consisting of at least one selected from the group consisting of %When,
(B) In the presence of the innermost hard layer polymer, 70 to 90% by mass of n-butyl acrylate, 10 to 30% by mass of styrene, and allyl, methallyl of α, β-unsaturated carboxylic acid copolymerizable therewith, Or the soft layer polymer 35-45 mass obtained by superposing | polymerizing a monomer mixture which consists of 1.5-3.0 mass% of graft-bonding monomers which consist of at least 1 sort (s) chosen from the group which consists of a crotyl ester. %When,
(C) In the presence of the innermost hard layer polymer and the soft layer polymer, 90 to 99% by mass of methyl methacrylate and 1 to 10% by mass of a monomer having 1 to 8 carbon atoms in the alkyl group. The outermost hard layer polymer 20-20% by mass obtained by polymerizing the mixture,
(D) The weight ratio of soft layer polymer / (innermost hard layer polymer + soft layer polymer) is 0.45 to 0.57,
(E) A multilayer structure acrylic polymer having an average particle size of 0.2 to 0.3 μm, and when the multilayer structure acrylic polymer is further fractionated with acetone,
(F) The graft ratio is 20 to 40% by mass,
(G) A multilayer acrylic polymer in which the tensile modulus of elasticity of the acetone insoluble part is 1000 to 4000 kg / cm ² .

In addition, examples of the rubbery polymer (III) include the following particles.
For example, Japanese Patent Publication No. 55-27576, Japanese Patent Publication No. 58-1694, Japanese Patent Publication No. 59-36645, Japanese Patent Publication No. 59-36646, Japanese Patent Publication No. 62-41241, Japanese Patent Publication No. 59-202213. Also, acrylic rubber particles having a three- to four-layer structure described in JP-A-63-27516, JP-A-51-129449, JP-A-52-56150, application S50-124647, etc. Can be used.

[Layer structure of rubbery polymer (III)]
As the number of layers of the rubbery polymer (III) is larger, it is possible to obtain a rubbery polymer whose elasticity is controlled within a suitable range, but from the viewpoint of production cost, Particles having a multilayer structure of three layers or more are preferable, and acrylic rubber particles having a multilayer structure of three layers or more are more preferable.
By using rubber particles having a multilayer structure equal to or greater than the above three-layer structure as the rubber polymer (III), thermal deterioration during molding and deformation of the rubber polymer due to heating are suppressed, and the heat resistance of the molded body is reduced. Tend to be maintained.

The rubbery polymer having a multilayer structure of three or more layers means a rubber particle having a multilayer structure in which a soft layer made of a rubbery polymer and a hard layer made of a glassy polymer are laminated, preferably hard from the inside. Particles having a three-layer structure formed in the order of layer (first layer) -soft layer (second layer) -hard layer (third layer).
By having the hard layer in the innermost layer and the outermost layer, deformation of the rubbery polymer tends to be suppressed, and by having a soft component in the central layer, good toughness tends to be imparted.

When the particle composed of three layers is formed of a multilayer structure graft copolymer, the multilayer structure graft copolymer is formed using, for example, methyl methacrylate and a monomer copolymerizable with the methyl methacrylate. Can be manufactured.
The monomer copolymerizable with methyl methacrylate is not limited to the following, but examples include known (meth) acrylic acid, (meth) acrylates other than methyl methacrylate, styrene, and α-methylstyrene. Monofunctional monomers such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, tri Examples thereof include polyfunctional monomers such as allyl isocyanurate, diallyl maleate, and divinylbenzene.
The said monomer can be used 1 type or in combination of 2 or more types as needed.

Specifically, when the rubber-containing copolymer particles have a three-layer structure, the copolymer that forms the innermost layer is 65 to 90% by mass of methyl methacrylate, and other copolymerizable with this. A copolymer using 10 to 35% by mass of a copolymerizable monomer is preferable.
From the viewpoint of appropriately controlling the refractive index, the other copolymerizable monomer copolymerizable with the methyl methacrylate is 0.1 to 5% by mass of an acrylate monomer and a single amount of an aromatic vinyl compound. It is preferable that 5-35 mass% of a body and 0.01-5 mass% of copolymerizable polyfunctional monomers are included.
In the case where the rubber-containing copolymer particles (III) have a three-layer structure, the acrylate monomer in the copolymer forming the innermost layer is not particularly limited. For example, acrylic acid n- Butyl and 2-hexyl acrylate are preferred.
As the aromatic vinyl compound monomer, the same monomers as those used in the methacrylic resin can be used. Preferably, the refractive index of the innermost layer is adjusted to adjust the refractive index of the visor of this embodiment. From the viewpoint of improving transparency, styrene or a derivative thereof is used.
The copolymerizable polyfunctional monomer is not particularly limited, but preferably ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1, Examples include 4-butanediol di (meth) acrylate, allyl (meth) acrylate, triallyl isocyanurate, diallyl maleate, and divinylbenzene. These may be used alone or in combination of two or more. You may use together. Among these, allyl (meth) acrylate is more preferable.

The second layer of the multi-layered graft copolymer composed of three layers, that is, the soft layer is a rubber-like copolymer exhibiting rubber elasticity, and is important for imparting excellent impact strength to the cast plate.
The second layer is preferably formed of, for example, a copolymer of an alkyl acrylate and a monomer copolymerizable with the alkyl acrylate.
The alkyl acrylate is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like, and one or more of these can be used in combination. N-butyl acrylate and 2-ethylhexyl acrylate are preferable.
In addition, other monomers copolymerizable with these alkyl acrylates are not particularly limited, and general monomers can be used. However, the acrylic resin can be adjusted by adjusting the refractive index of the second layer. From the viewpoint of improving transparency by adjusting to (A), styrene or a derivative thereof is preferably used.

In the case where the rubber-containing copolymer particles (III) have a three-layer structure, the copolymer forming the outermost layer is 70 to 100% by mass of methyl methacrylate, and other copolymers copolymerizable with this. It is preferable that it contains 0-30 mass% of a monomer.
Although it does not specifically limit as another copolymerizable monomer which can be copolymerized with methyl methacrylate which forms the said outermost layer, N-butyl acrylate and 2-hexyl acrylate are mentioned as a preferable thing.

When rubbery polymer (III) is comprised from three layers, rubbery polymer (III) may contain the rubber-like polymer which has a crosslinked structure.
The rubbery polymer having a crosslinked structure preferably forms the second layer, and a rubbery polymer having a crosslinked structure formed by copolymerizing a polyfunctional monomer can be applied. .
The cross-linked structure in the rubber-like polymer is necessary for imparting appropriate rubber elasticity and maintaining its form in a dispersed state without dissolving in the monomer mixture.
As the polyfunctional monomer for forming the crosslinked structure, compounds exemplified as those copolymerizable with methyl methacrylate and methyl acrylate can be used, and the amount used is 0 with respect to the entire second layer. It is preferable that it is 1-5 mass%. When the amount of the polyfunctional monomer used is less than 0.1% by mass, a sufficient crosslinking effect cannot be obtained. Absent. Further, if the amount used is less than 0.1% by mass, the rubbery polymer is dissolved or greatly swelled in the cast polymerization step described later, which is not preferable because the rubber elastic body cannot be maintained.

Furthermore, it is preferable to use a polyfunctional grafting agent for forming a graft bond that closes the affinity with the polymer of the third layer in the second layer.
The polyfunctional grafting agent is a polyfunctional monomer having a different functional group and is not limited to the following, but examples include allyl esters such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid. Of these, allyl acrylate and allyl methacrylate are preferred. It is preferable that the usage-amount of a polyfunctional grafting agent is the range of 0.1-3 mass% with respect to the whole 2nd layer. If the amount of the polyfunctional grafting agent used is less than 0.1% by mass, a sufficient graft effect cannot be obtained, and if it exceeds 3% by mass, the rubber elasticity is lowered, which is not preferable.

  In the polymerization of the third layer (outermost layer), the molecular weight can be adjusted using a chain transfer agent in order to improve the affinity with the methacrylic resins (I) and (II).

In order to improve the transparency of the visor of this embodiment, it is necessary to match the refractive indexes of the dispersed rubbery polymer (III) and the methacrylic resins (I) and (II). As described above, in the second layer, when alkyl acrylate is used as a main component, it is extremely difficult to make the refractive index of the second layer completely coincide with that of the methacrylic resins (I) and (II). . In order to match the refractive index, for example, in the second layer, when alkyl acrylate and styrene or its derivatives are copolymerized, the refractive index becomes substantially equal in a certain temperature range and the transparency is improved. A refractive index shift occurs and transparency is deteriorated.
As a means for avoiding this, there is a method of providing a first layer whose refractive index is substantially the same as that of the methacrylic resins (I) and (II). Further, reducing the thickness of the second layer is also effective in preventing the deterioration of transparency.

The rubbery polymer (III) is preferably obtained by emulsion polymerization.
Specifically, when the rubber polymer (III) is composed of three layers as described above, the first monomer mixture is first added in the presence of an emulsifier and an initiator to complete the polymerization. Then, the second layer monomer mixture is added to complete the polymerization, and then the third layer monomer mixture is added to complete the polymerization. Can be obtained as a latex.
This rubbery polymer (III) can be recovered from the latex as a powder by a known method such as salting out, spray drying, freeze drying and the like.
When the rubber polymer (III) is a polymer composed of three layers, aggregation of the powders can be avoided by providing a hard resin component in the third layer.

Moreover, it is preferable that the average particle diameter of rubber-like polymer (III) is 0.05-1 micrometer. More preferably, they are 0.05 micrometer-0.7 micrometer, More preferably, they are 0.05 micrometer-0.5 micrometer, More preferably, they are 0.05 micrometer-0.4 micrometer, More preferably, they are 0.05 micrometer-0.3 micrometer.
When the average particle diameter of the rubber polymer (III) is 0.05 μm or more, sufficient impact strength tends to be obtained, and when it is 1 μm or less, a certain value or more (the acetone insoluble part is 65% by mass or more). When the amount of the above is blended, the characteristics as a rubber elastic body can be expressed, and it is possible to prevent the appearance of fine ripples on the surface of the molded product of the methacrylic resin composition finally obtained. Specularity can be obtained, and further, when thermoformed, a decrease in surface gloss can be suppressed in the stretched portion, and transparency can be ensured.

As a method for measuring the average particle size of the rubbery polymer (III), a conventionally known method can be used, and examples thereof include the following methods (1) and (2).
(1) After cutting out a part of the molded product of the methacrylic resin composition with a circular saw, a sample for observation by a RuO ₄ (ruthenic acid) dyed ultrathin section method was prepared, and manufactured by Hitachi, Ltd. Type electron microscope model: Take a picture after observing the cross section of the dyed rubber particles using H-600 type. The average particle diameter of rubber particles is obtained by measuring the diameter of 20 representative particles printed at a high magnification on a scale and obtaining the average value of the diameters of the particles.
Also, (2) the emulsion of the rubber polymer (III) is sampled, diluted with water to a solid content of 500 ppm, and a wavelength of 550 nm using a UV 1200 V spectrophotometer (manufactured by Shimadzu Corporation). From this value, the average particle size is determined using a calibration curve prepared by measuring the absorbance in the same manner for a sample whose particle size was measured from a transmission electron micrograph.
In the measurement methods (1) and (2), almost the same particle diameter measurement values can be obtained.

  In the visor of this embodiment, when the rubbery polymer (III) is contained, the blending amount of the rubbery polymer (III) in the manufacturing process stage is considered in consideration of fluidity, impact resistance, and mechanical properties. The rubber polymer (III) is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the methacrylic resin. More preferably, it is 1-150 mass parts, More preferably, it is 1-120 mass parts, More preferably, it is 5-100 mass parts.

The content of the rubber polymer (III) can be determined by measuring the amount of the acetone insoluble part.
That is, a part of a methacrylic resin composition pellet or a molded piece is placed in a mass (W1) after precise weighing and a predetermined centrifuge tube, and then dissolved by adding acetone to remove the acetone soluble part. The solvent is removed by a vacuum dryer and cooled, and the weighed residue is defined as an acetone insoluble part. The mass after precise weighing of the acetone insoluble part is defined as (W2).
The blending amount of rubber polymer (III) does not match the acetone insoluble part, and even if the rubber particle structure (outermost hard layer: dissolved in acetone) is the same size, the physical properties obtained are different, so impact resistance The rubbery polymer (III) that contributes to is defined as an acetone insoluble part.
From the following formula, the acetone-insoluble part (mass%) in the methacrylic resin composition: (X), that is, the content of the rubber-like polymer (III) that contributes to impact resistance can be calculated.
Acetone insoluble part (X) = W2 / W1 × 100

  In the visor of the present embodiment, the acetone insoluble part content is 1 to 65% by mass in consideration of optical properties [(total light transmittance, haze (cloudiness value)], fluidity, impact resistance, and mechanical strength. More preferably, it is 1-60 mass%, More preferably, it is 1-54 mass%, More preferably, it is 4-50 mass%.

  In the visor of this embodiment, from the viewpoint of high transparency, transparency, particularly transparency temperature dependency, the refractive index of the methacrylic resins (I) and (II) and the refractive index of the rubbery polymer (III). Is preferably 0.015 or less, more preferably 0.012 or less, and still more preferably 0.01 or less.

<Other resins>
As for other resins to be combined with the methacrylic resin described above, known thermoplastic resins can be used as long as they can exhibit the characteristics required for the visor of the present embodiment.
Examples of the thermoplastic resin include, but are not limited to, polyethylene resins, polypropylene resins, polystyrene resins, syndiotactic polystyrene resins, polycarbonate resins, ABS resins, acrylic resins, Polyalkylene arylates such as AS resin, BAAS resin, MBS resin, AAS resin, biodegradable resin, polycarbonate-ABS resin alloy, polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate Resins: Polyamide resins, polyphenylene ether resins, polyphenylene sulfide resins, phenol resins, and the like.
In particular, AS resin and BAAS resin are preferable from the viewpoint of improving fluidity, ABS resin and MBS resin are preferable from the viewpoint of improving impact resistance, and polyester resin is preferable from the viewpoint of improving chemical resistance.
Polyphenylene ether resins, polyphenylene sulfide resins, phenol resins, and the like are preferable from the viewpoint of improving flame retardancy.
Polycarbonate resins are preferred when it is necessary to impart heat resistance, impact resistance or optical properties.
Furthermore, the acrylic resin has good compatibility with the methacrylic resin described above, and is preferable when adjusting characteristics such as fluidity and impact resistance while maintaining transparency.
The various thermoplastic resins may be used alone or in combination of two or more resins.

In the visor of the present embodiment, when the above-mentioned methacrylic resin and the other resin are used in combination, these blending ratios may be in a range where the effects of the present invention can be exhibited, but impart characteristics. Considering the effect, the blending ratio of the other resin is preferably 50% by mass or less with respect to 100% by mass of the total amount of the methacrylic resins (I) and (II) and the other resin. More preferably, it is 45 mass%, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.
In consideration of the effect of imparting properties when other resins are blended, the lower limit of the blending amount when blending other resins is preferably 0.1% by mass or more, more preferably 1% by mass or more, and Preferably it is 2 mass% or more, More preferably, it is 3 mass% or more, More preferably, it is 5 mass% or more.
The type and content of other resins can be appropriately selected according to the effects expected when used in combination with other resins.

<Additives>
A predetermined additive may be added to the methacrylic resin used in the visor of the present embodiment in order to impart various characteristics such as rigidity and dimensional stability.
Examples of additives include, but are not limited to, various stabilizers such as UV absorbers, heat stabilizers, and light stabilizers; plasticizers (paraffinic process oils, naphthenic process oils, aromatics) Process oil, paraffin, organic polysiloxane, mineral oil), flame retardants (eg, phosphorus compounds such as organic phosphorus compounds, red phosphorus, inorganic phosphates, halogens, silicas, silicones, etc.), flame retardant aids (For example, antimony oxides, metal oxides, metal hydroxides, etc.), curing agents (diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diethylaminopropylamine, 3,9-bis (3-aminopropyl) ) -2,4,8,10-tetraoxaspiro [5,5] undecane, mensendiamine, isophoro Amines such as diamine, N-aminoethylpiperazine, m-xylenediamine, m-phenylenediamine, diaminophenylmethane, diaminodiphenylsulfone, dicyandiamide, adipic dihydrazide, and phenol resins such as phenol novolac resin and cresol novolac resin , Liquid polymercaptan, polymer sulfide such as polysulfide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, methylcyclohexene Tetracarboxylic anhydride, dodecyl succinic anhydride, trimellitic anhydride, chlorendic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis Acid anhydrides such as (anhydrotrimate)), curing accelerators (2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2- Heptadecylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, organic phosphines such as triphenylphosphine and tributylphosphine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, 2,4,6-tris (diamino) Tertiary amines such as methyl) phenol and tetramethylhexanediamine, boron salts such as triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate and triethylaminetetraphenylborate, 1,4-benzoyl , 1,4-naphthoquinone, 2,3-dimethyl-1,4-benzoquinone, 2,6-dimethylbenzoquinone, quinoid compounds such as 2,3-dimethoxy-1,4-benzoquinone), antistatic agents (for example, , Polyamide elastomer, quaternary ammonium salt system, pyridine derivative, aliphatic sulfonate, aromatic sulfonate, aromatic sulfonate copolymer, sulfate ester salt, polyhydric alcohol partial ester, alkyldiethanolamine, alkyldiethanolamide , Polyalkylene glycol derivatives, betaines, imidazoline derivatives, etc.), conductivity imparting agents, stress relieving agents, mold release agents (alcohols, esters of alcohols and fatty acids, alcohols and esters of dicarboxylic acids, silicone oils, etc.), Crystallization accelerators, hydrolysis inhibitors, lubricants (eg Higher fatty acids such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and metal salts thereof, higher fatty acid amides such as ethylene bisstearamide), impact imparting agents, slidability improvers ( Hydrocarbons such as low molecular weight polyethylene, higher alcohols, polyhydric alcohols, polyglycols, polyglycerols, higher fatty acids, higher fatty acid metal salts, fatty acid amides, esters of fatty acids and fatty alcohols, full of fatty acids and polyhydric alcohols Esters or partial esters, full esters or partial esters of fatty acids and polyglycols, silicones, fluororesins, etc.), compatibilizers, nucleating agents, fillers and other reinforcing agents, flow control agents, dyes (nitroso dyes, nitro dyes) , Azo dye, stilbene azo dye, ketoimine dye, trifer Nylmethane dye, xanthene dye, acridine dye, quinoline dye, methine / polymethine dye, thiazole dye, indamine / indophenol dye, azine dye, oxazine dye, thiazine dye, sulfur dye, aminoketone / oxyketone dye, anthraquinone dye, indigoid dye, phthalocyanine Dyes such as dyes), sensitizers, colorants (titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine, cobalt blue, chromium oxide, spinel green, lead chromate pigments, cadmium pigments, etc. Pigments, azo lake pigments, benzimidazolone pigments, diarylide pigments, azo pigments such as condensed azo pigments, phthalocyanine pigments such as phthalicyanine blue and phthalocyanine green, isoindolinone pigments, quinophthalone pigments, quinacrid Pigments, perylene pigments, anthraquinone pigments, perinone pigments, organic pigments such as condensed polycyclic pigments such as dioxazine violet, flake-like aluminum metallic pigments, spherical shapes used to improve weld appearance Aluminum pigments, mica powders for pearl-like metallic pigments, other metallic pigments such as glass coated inorganic polyhedral particles such as metal plating or sputtering), thickeners, anti-settling agents, anti-sagging agents, fillers (Fibrous reinforcing agents such as glass fiber and carbon fiber, as well as glass beads, calcium carbonate, talc, clay, etc.), antifoaming agents (silicone-based antifoaming agents, surfactants, polyethers, higher alcohols, etc.) Defoaming agents, etc.), coupling agents, light diffusing fine particles, rust preventives, antibacterial / antifungal agents, antifouling agents, conductive polymers, rubber polymers, etc. It is below.

Examples of the light diffusing fine particles include, but are not limited to, inorganic fine particles such as alumina, titanium oxide, calcium carbonate, barium sulfate, silicon dioxide, and glass beads, styrene crosslinked beads, MS crosslinked beads, and siloxane. Organic fine particles such as system cross-linked beads.
Further, hollow cross-linked fine particles made of highly transparent resin materials such as acrylic resin, polycarbonate resin, MS resin, and cyclic olefin resin, hollow fine particles made of glass, and the like can also be used as the light diffusing fine particles.
As the inorganic fine particles, alumina, titanium oxide, and the like are more preferable from the viewpoints of diffusibility and availability.
Further, the light diffusing fine particles may be used alone or in combination of two or more.
Here, the refractive index of the light diffusing fine particles is preferably 1.3 to 3.0, more preferably 1.3 to 2.5, and still more preferably 1.3 to 2.0.
When the refractive index is 1.3 or more, practically sufficient scattering is obtained, and when it is 3.0 or less, when the visor of this embodiment is used for a member near the lamp, Scattering can be suppressed and the occurrence of uneven brightness and unevenness of the emitted light color tone can be effectively prevented.
The refractive index is a value at a temperature of 20 ° C. based on the D line (589 nm).
As a method for measuring the refractive index of the light diffusing fine particles, for example, immersing the light diffusing fine particles in a liquid whose refractive index can be changed little by little, and observing the interface of the light diffusing fine particles while changing the refractive index of the liquid. In addition, there is a method of measuring the refractive index of the liquid when the light diffusing fine particle interface becomes unclear. An Abbe refractometer or the like can be used to measure the refractive index of the liquid.

The average particle diameter of the light diffusing fine particles is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm, still more preferably 0.3 to 10 μm, and still more preferably 0.4 to 5 μm. .
An average particle diameter of 20 μm or less is preferable because light loss due to back reflection or the like is suppressed and incident light can be efficiently diffused to the light emitting surface side. In addition, it is preferable that the average particle diameter is 0.1 μm or more because emitted light can be diffused and desired surface emission luminance and diffusibility can be obtained.

  Further, the content of the light diffusing fine particles in the methacrylic resin composition is 0.0001 to 0.03 mass with respect to 100 parts by mass of the methacrylic resin from the viewpoint of the expression of the light diffusing effect and the uniformity of surface emission. Part is preferable, and more preferably 0.0001 to 0.01 part by mass.

Examples of the heat stabilizer include, but are not limited to, hindered phenol antioxidants and phosphorus antioxidants. From the viewpoint of the effect of imparting thermal stability to the resin, hindered Phenol antioxidants are preferred.
In the visor of the present embodiment, for example, when a long molded product such as a meter cover or a tail lamp cover is used, if a volatile component is included, a weld line tends to be easily generated during molding. For this reason, from the viewpoint of suppression of weld lines and suppression of silver streak, the vapor pressure (P) of the heat stabilizer at 20 ° C. is preferably 1.0 × 10 ⁻⁴ Pa or less, and 1.0 × 10 ⁻ It is more preferably ⁵ Pa or less, and further preferably 1.0 × 10 ⁻⁶ Pa or less.

  The content of the heat stabilizer only needs to be an amount that exhibits the effect of the present invention. If the content is excessive, problems such as bleeding out during processing may occur. It is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less, and still more preferably 0.01 parts by mass with respect to parts by mass. Part to 0.8 parts by mass, particularly preferably 0.01 parts by mass to less than 0.5 parts by mass.

Examples of the heat stabilizer include, but are not limited to, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3 ′, 3 ″, 5 , 5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -O-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hex Methylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3 , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylin) methyl] -1, 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine 2-ylamine) phenol, acrylic acid 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl, acrylic acid 2-tert- Butyl-4-methyl-6- (2-hydroxy-3-tert-butyl) (Lu-5-methylbenzyl) phenyl and the like.
In particular, pentaerythritol terakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, Acrylic acid 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl is preferred.

The hindered phenolic antioxidant as the heat stabilizer may be a commercially available phenolic antioxidant, and such a commercially available phenolic antioxidant is limited to the following. However, for example, Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals), Irganox 1076 (Irganox 1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by Ciba Specialty Chemicals), Irganox 1330 (Irganox 1330: 3, 3 ′, 3 ″ 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″- (Mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by Ciba Specialty Chemicals), Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-t-butyl) -4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by Ciba Specialty Chemicals), Irganox 3125 (Irganox 3125, Ciba Specialty) Chemicals), Sumilizer BHT (Sumilizer BHT, manufactured by Sumitomo Chemical), Cyanox 1790 (Cyanox 1790, manufactured by Cytec), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical), Sumilizer GS (Sumilizer GS: Acrylic acid 2 -[1- (2 -Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl, manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GM (2-tert-butyl-4-methyl acrylate) -6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl (manufactured by Sumitomo Chemical), vitamin E (manufactured by Eisai) and the like.
Among these commercially available phenolic antioxidants, Irganox 1010, Irganox 1076, Sumilizer GS, and the like are preferable from the viewpoint of imparting thermal stability with the resin. These may be used alone or in combination of two or more.

The phosphorus-based antioxidant as the heat stabilizer is not limited to the following, and examples thereof include tris (2,4-di-t-butylphenyl) phosphite and bis (2,4- Bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, tetrakis (2,4-di-t-butylphenyl) (1,1-biphenyl) -4,4′-diylbisphos Phonite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4 -Dicumylphenyl) pentaerythritol-diphosphite, tetrakis (2,4-t-butylphenyl) (1,1-biphenyl) -4,4'-diylbisphosphonate , Di-t-butyl-m-cresyl-phosphonite, 4- [3-[(2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine Pin) -6-yloxy] propyl] -2-methyl-6-tert-butylphenol and the like.
Furthermore, a commercially available phosphorus antioxidant may be used as the phosphorus antioxidant. Examples of such commercially available phosphorus antioxidants are not limited to the following, but include Irgaphos 168 ( Irgafos 168: Tris (2,4-di-t-butylphenyl) phosphite, manufactured by Ciba Specialty Chemicals, Irgafos 12 (Irgafos 12: Tris [2-[[2,4,8,10-tetra- t-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6-yl] oxy] ethyl] amine, manufactured by Ciba Specialty Chemicals, Irgafos 38 (Irgafos 38: Bis (2 , 4-Bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by Ciba Specialty Chemicals) , ADK STAB 329K (ADK STAB 329K, manufactured by Asahi Denka), ADK STAB PEP36 (ADK STAB PEP36, manufactured by Asahi Denka), ADK STAB PEP-8 (ADK STAB PEP-8, manufactured by Asahi Denka), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (manufactured by Weston 619G, manufactured by GE), Ultranox 626 (manufactured by Ultranox 626, manufactured by GE), Sumilizer GP (Sumilizer GP: 4- [3-[(2,4,8, 10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin) -6-yloxy] propyl] -2-methyl-6-tert-butylphenol, manufactured by Sumitomo Chemical Co., Ltd.) Can be mentioned.
These phosphorus antioxidants may be used alone or in combination of two or more.

Further, in the visor of the present embodiment, in order to obtain practically sufficient thermal stability, when the blending ratio of the thermal stabilizer to 100 parts by mass of the methacrylic resin is (Y) / part by mass, It is preferable that the compounding ratio (Y) of the acid ester monomer unit, the structural unit (B) having a ring structure in the main chain, and the heat stabilizer satisfy the following formula (i).
(Y) ≧ 0.053 × [methacrylic acid ester monomer unit content / (B) content] −0.4 (i)
In addition, when the methacrylic resin contained in the visor of this embodiment is only the methacrylic resin (I) described above, it is preferable that the following formula (i-1) is satisfied, and the methacrylic resin (I described above) is satisfied. ) And (II), the following formula (i-2) is preferably satisfied.
(Y) ≧ 0.053 × [(A) content / (B) content] −0.4 Formula (i-1)
(Y) ≧ 0.053 × [(A) + (A ′) content / (B) content] −0.4 Formula (i-2)

As described above, the methacrylic resin (I) used as the material of the visor of the present embodiment includes the structural unit (B) having a ring structure in the main chain.
By including the structural unit (B) having a ring structure in the main chain, thermal decomposition of the methacrylic resin is suppressed when the methacrylic resin is exposed to high temperature conditions such as molding, and the amount of volatile components generated The effect of reducing is obtained.
That is, the content of the structural unit (B) having a ring structure in the main chain is changed to the methacrylic acid ester monomer unit ((A) contained in the methacrylic resin (I) and the methacrylic monomer used as necessary. By increasing with respect to the total amount of the methacrylic ester monomer units (A ′) of the resin (II), it is possible to reduce the amount of the above-mentioned heat stabilizer added.
On the other hand, if the ratio of the methacrylic acid ester monomer unit is large with respect to the content of the structural unit (B) having a ring structure in the main chain, the thermal decomposition of the methacrylic resin proceeds. It is necessary to increase the amount of heat stabilizer added.
Specifically, using methyl methacrylate (MMA) and maleimide-based structural unit (MI) shown in the examples described later, this corresponds to MMA / MI (methacrylic acid ester-based monomer unit content / (B) content. And the amount of the thermal stabilizer necessary for obtaining practically excellent thermal stability, the results of the above formulas (i), (i-1), and (i-2) By applying the amount of methacrylic resin and the amount of the thermal stabilizer that satisfy the conditions of (i), (i-1), and (i-2), the thermal stability excellent in practical use is derived. It turns out that it is obtained.
At this time, “practically excellent thermal stability” means that the methacrylic resin decomposes when held at 270 ° C. for 30 minutes, as described in the examples described later, thereby reducing the mass. It means that the amount is 5% or less.
If a thermal stabilizer is contained so as to satisfy the above formulas (i), (i-1), and (i-2), a practically excellent thermal stability can be obtained, and an excessive blend of thermal stabilizers can be obtained. It can also be suppressed.

From the viewpoint of obtaining high thermal stability, (Y) ≧ 0.053 × [methacrylic acid ester monomer unit content / (B) content] −0.35, more preferably (Y). ≧ 0.053 × [methacrylic acid ester monomer unit content / (B) content] −0.3, more preferably (Y) ≧ 0.053 × [methacrylic acid ester monomer unit content Amount / (B) content] -0.25.
If it is the said range, the high thermal stability suitable as a visor can be hold | maintained.

Examples of the ultraviolet absorber include, but are not limited to, for example, benzotriazole compounds, benzotriazine compounds, benzoate compounds, benzophenone compounds, oxybenzophenone compounds, phenol compounds, oxazole compounds, Examples include malonic acid ester compounds, cyanoacrylate compounds, lactone compounds, salicylic acid ester compounds, and benzoxazinone compounds.
In particular, from the viewpoint of compatibility with the resin, benzotriazole compounds and benzotriazine compounds are preferable. These may be used alone or in combination of two or more.
From the viewpoint of ensuring good moldability of the methacrylic resin composition, the ultraviolet absorber preferably has a vapor pressure (P) at 20 ° C. of 1.0 × 10 ⁻⁴ Pa or less. It is more preferably 10 ⁻⁶ Pa or less, and further preferably 1.0 × 10 ⁻⁸ Pa or less.
Here, good moldability means that, for example, when a film is formed, there is little adhesion of a low molecular compound to a roll. When it adheres to the roll, it re-adheres to the surface, which causes the appearance to deteriorate and the optical properties to deteriorate, so satisfy the above vapor pressure (P) value and obtain good moldability. Is preferred.

Further, the melting point (Tm) of the ultraviolet absorber is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, further preferably 130 ° C. or higher, and more preferably 160 ° C. or higher. More preferred.
The ultraviolet absorber preferably has a weight reduction rate of 50% or less, more preferably 30% or less, and more preferably 15% or less when the temperature is increased from 23 ° C. to 260 ° C. at a rate of 20 ° C./min. Is more preferably 10% or less, still more preferably 5% or less.
The blending amount of the ultraviolet absorber may be an amount that exhibits the effect of the present invention, but if it is excessively added, a problem such as bleeding out at the time of processing may occur. The amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less, and still more preferably 0.8 parts by mass or less with respect to 100 parts by mass of the resin. 01 parts by mass or more and 0.8 parts by mass or less.

(Processing of methacrylic resin and methacrylic resin composition)
Examples of methods for processing a methacrylic resin composition, or mixing various additives of the methacrylic resin and other resins to process a methacrylic resin composition include, for example, an extruder, a heating roll, a kneader, and a roller mixer. And a kneading method using a kneading machine such as a Banbury mixer.
Among these, kneading with an extruder is preferable in terms of productivity.
The kneading temperature may be in accordance with the preferred processing temperature of the polymer constituting the methacrylic resin and other resins to be mixed, and is generally in the range of 140 to 300 ° C, preferably in the range of 180 to 280 ° C.

[Manufacturing method of visor]
A visor can be obtained by molding the above methacrylic resin alone or by molding the methacrylic resin composition containing the methacrylic resin.
As a method for manufacturing the visor, known methods such as injection molding, sheet molding, blow molding, injection blow molding, inflation molding, T-die molding, press molding, extrusion molding, foam molding, etc. can be applied, Secondary processing molding methods such as vacuum molding can also be used.
A method of kneading and producing a methacrylic resin composition using a kneader such as a heating roll, kneader, Banbury mixer, extruder, etc., cooling, pulverizing, and further molding by transfer molding, injection molding, compression molding, etc. Can also be cited as an example.

[Characteristics as a visor]
The visor is attached to the outside of the vehicle and is generally exposed to high-temperature and high-humidity conditions. Therefore, the visor is required to have excellent moisture and heat resistance with almost no distortion under high-temperature and high-humidity conditions. In addition, thinning of the molded body is required due to the demand for weight reduction, and accordingly, higher heat resistance and molding processability are required. In particular, in a visor application, it is necessary to mold a long molded body, but high heat resistance and molding processability are required for thinning.

(Heat-resistant)
The VICAT softening temperature in the visor of the present embodiment is preferably 110 ° C. or higher from the viewpoint of suppressing problems such as distortion of the molded body during actual use. More preferably, it is 112 degreeC or more, More preferably, it is 113 degreeC or more, More preferably, it is 115 degreeC or more, More preferably, it is 117 degreeC or more, Most preferably, it is 120 degreeC or more.
The VICAT softening temperature can be measured according to ISO 306 B50, and specifically, can be measured by the method described in Examples described later.

(transparency)
The visor of this embodiment preferably has a total light transmittance of 70% or more at a thickness of 3 mm from the viewpoint of visibility. More preferably, it is 75% or more, More preferably, it is 80% or more.
Although it is preferable that the total light transmittance is high, practically sufficient visibility can be secured even at 94% or less.
Specifically, the transparency can be measured by the method described in Examples described later.
Moreover, it can also be colored and used for a visor use. In that case, the total light transmittance at a thickness of 3 mm is preferably 10% or more from the viewpoint of visibility, more preferably 15% or more, still more preferably 20% or more, and even more preferably 25% or more. is there.
The total light transmittance can be measured by the method described in Examples described later.

(Thickness)
The thickness of the visor of the present embodiment may be appropriately selected in consideration of weight, strength, and moldability, and specifically, 0.1 to 5 mm is preferable. More preferably, it is 0.5-4 mm, More preferably, it is 0.5-3 mm, More preferably, it is 0.5-2 mm.

(Moisture and heat resistance)
When using a visor, it may be placed under hot and humid conditions. In particular, in an environment that is easily exposed to direct sunlight, it is placed under high-temperature and high-humidity conditions, and conventional methacrylic resins may cause defects such as warpage and distortion.
The visor of the present embodiment is preferably free from defects such as warpage and distortion when left for 500 hours under conditions of a set temperature of 70 ° C. and a set humidity of 95% as an evaluation of heat and moisture resistance.

(Scratch resistance)
Since the visor is arranged at the upper part of the side window of the vehicle, it is preferable to have high scratch resistance since the appearance during use is also important.
The visor of this embodiment preferably has a pencil hardness of H or higher as the surface hardness.
Specifically, the scratch resistance of the visor can be evaluated by the method described in Examples described later.

(Molding processability)
Since the visor is a long shaped molded body depending on the application, it is preferable that the visor has high molding fluidity.
Furthermore, visors are required to be thin for weight reduction, but in order to reduce the thickness of the molded body, it is effective to increase the molding temperature and improve the fluidity. There is a possibility that silver streak and jetting may occur by raising.
Even when the methacrylic resin or methacrylic resin composition used for producing the visor of the present embodiment is molded by raising the molding temperature and lowering the melting temperature in order to eliminate molding distortion, defects such as silver are present. It is preferable not to come out. Specifically, when molding is performed continuously for 50 shots at a barrel temperature of 290 ° C. and a mold temperature of 60 ° C., it is preferable that molding defects such as silver streaks are hardly seen.
Specifically, the moldability can be evaluated by the method described in Examples described later.

(Thermal stability)
When the visor of this embodiment is manufactured by injection molding, the visor is often a large molded piece, and a relatively large injection molding machine may be used, and the resin may stay in a molten state in the molding machine. is there. At that time, since the resin stays at a high temperature for a long time, the resin material is required to be hardly thermally decomposed.

Specifically, the weight loss rate when held at about 270 ° C. for 30 minutes is preferably 5% or less, more preferably 3% or less, still more preferably 1.0% or less, and even more preferably 0.00. 5% or less.
About the thermal decomposition amount at the time of holding | maintenance of 270 degreeC / 30 minutes, it can measure by the method described in the Example mentioned later.

When it is necessary to mold the visor of this embodiment with a thin wall, it is necessary to perform molding at a high temperature, and high thermal stability is required.
From this viewpoint, the thermal decomposition starting temperature of the methacrylic resin or methacrylic resin composition is preferably 300 ° C. or higher. More preferably, it is 310 degreeC or more, More preferably, it is 320 degreeC or more, More preferably, it is 325 degreeC or more, More preferably, it is 330 degreeC or more.
Specifically, the thermal decomposition start temperature can be measured by the method described in the examples described later.

As described above, in order to prevent thermal decomposition of the methacrylic resin or methacrylic resin composition and to have practically excellent thermal stability, the methacrylic resin (I ), The amount of the structural unit (B) having a ring structure in the main chain is increased, and the amount of copolymerization of the methacrylic acid ester monomer units (component (A) and component (A ′)) is relatively increased. It is effective to reduce.
However, if the ratio of the component (B) to the methacrylic acid ester monomer units (component (A) and component (A ′)) is too high, characteristics such as molding fluidity and surface hardness required as a visor can be obtained. Therefore, it is necessary to determine the ratio of the ((A) component and the (A ′) component) and the (B) component in consideration of the balance of these characteristics.
Increasing the copolymerization ratio of the structural unit (B) having a ring structure in the main chain is effective in terms of suppressing a decomposition reaction due to depolymerization when exposed to a high temperature. When the ratio to the ester monomer units (component (A) and component (A ′)) is increased, sufficient thermal stability can be imparted even if the amount of the thermal stabilizer is reduced.
On the other hand, if the proportion of the methacrylic acid ester monomer units (component (A) and component (A ′)) is relatively large, the amount of thermal decomposition in a high temperature environment increases. A heat stabilizer may be added from the viewpoint of suppressing thermal decomposition, but adding too much may cause a decrease in heat resistance and may cause problems such as bleeding out during molding.

In order to obtain the characteristics required as a visor, as described above, when the blending ratio of the heat stabilizer to 100 parts by mass of the methacrylic resin is (Y: parts by mass), the thermal decomposition is suppressed and molded at a high temperature. From the viewpoint of balance between processability and heat resistance, it is preferable that the blending ratio of the methacrylic acid ester monomer unit, the structural unit (B) having a ring structure in the main chain, and the thermal stabilizer satisfies the following formula (i). .
(Y) ≧ 0.053 × [methacrylic acid ester monomer unit content / (B) content] −0.4 (i)
In addition, when the methacrylic resin contained in the visor of this embodiment is only the methacrylic resin (I) described above, it is preferable that the following formula (i-1) is satisfied, and the methacrylic resin (I described above) is satisfied. ) And (II), the following formula (i-2) is preferably satisfied.
(Y) ≧ 0.053 × [(A) content / (B) content] −0.4 Formula (i-1)
(Y) ≧ 0.053 × [(A) + (A ′) content / (B) content] −0.4 Formula (i-2)
More preferably, (Y) ≧ 0.053 × [methacrylic acid ester monomer unit content / (B) content] −0.35, and further preferably (Y) ≧ 0.053 × [methacrylic acid ester. Monomer unit content / (B) content] −0.3, and even more preferably (Y) ≧ 0.053 × [methacrylic acid ester monomer unit content / (B) content] − 0.27, more preferably (Y) ≧ 0.053 × [methacrylic acid ester monomer unit content / (B) content] −0.25.

(Impact resistance)
Since the visor of this embodiment is used as a vehicle exterior part, high impact strength may be required. Specifically, the Charpy impact strength (without notch) measured in accordance with the IOS 179 / 1eU standard is preferably 15 kJ / m ² or more. More preferably 15 kJ / m ² or more 20 kJ / m less than ^2, more preferably 20 kJ / m ² or more 25 kJ / m less than ^2, particularly preferably 25 kJ / m ² or more.

[Use]
The visor of this embodiment can be suitably used for vehicle visor applications.
For example, it can be suitably used in vehicle visor applications such as a side window visor attached to the upper part of an automobile side window, a weather guard, and a meter visor attached to the front of a motorcycle.

  Hereinafter, although a specific Example and a comparative example are given and demonstrated, this invention is not limited to these.

〔material〕
It shows below about the raw material used in the Example and comparative example which are mentioned later.
(A) component:
(A-1): Methyl methacrylate (MMA)
: Asahi Kasei Chemicals Co., Ltd. (2.5 ppm of 2,4-di-6-tert-butylphenol as a polymerization inhibitor, manufactured by Chugai Trading Co., Ltd.) Added)
(A-2): cyclohexyl methacrylate: manufactured by Asahi Kasei Chemicals Corporation (A-3): phenyl methacrylate: manufactured by Wako Pure Chemical Industries, Ltd.

(B) component:
(B-1): N-phenylmaleimide (NPMI)
: Nippon Shokubai Co., Ltd. (B-2): N-cyclohexylmaleimide (NCyMI)
: Nippon Catalyst Co., Ltd.

(C) component:
(C-1): Styrene (St)
: Asahi Kasei Chemicals Corporation (C-2-1): Methyl acrylate (MA)
: Made by Mitsubishi Chemical Corporation (14-ppm of 4-methoxyphenol made by Kawaguchi Chemical Industry is added as a polymerization inhibitor)
(C-2-2): Ethyl acrylate (EA)
: Made by Mitsubishi Chemical Corporation (C-3): Acrylonitrile (AN)
: Asahi Kasei Chemicals Corporation

(D) component:
(D-1): Maleic anhydride (MAH)
: Mitsui Chemicals, Inc.

(E) component:
(E-1): Irganox 1076: Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate: manufactured by Ciba Specialty Chemicals (E-2): Irganox 1010: Penta Erythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
: Ciba Specialty Chemicals (E-3): Sumilizer GS: 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl acrylate] -4,6-di-tert acrylate -Pentylphenyl: manufactured by Sumitomo Chemical Co., Ltd. (E-4): Sumilizer GM: 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl acrylate: Sumitomo Chemical (E-5): Irgaphos 168: Tris (2,4-di-t-butylphenyl) phosphite: Ciba Specialty Chemicals

(Other ingredients):
n-octylmercaptan (NOM)
: Lauroyl peroxide (LPO) manufactured by Arkema Co., Ltd.
: Nippon Oil & Fats Co., Ltd. Tricalcium phosphate
: Nihon Kagaku Kogyo Co., Ltd., used as a suspending agent Calcium calbonate
: Shiraishi Kogyo Co., Ltd., used as a suspending agent Sodium lauryl sulfate
: Wako Pure Chemical Industries, Ltd., used as a suspension aid
2- (2-Hydroxy-5-methylphenyl) benzotriazole (2- (2H-Benzotriazol-2-yl) -p-cresol
： Johoku Chemical Co., Ltd. JF77, used as UV absorber

(Calculation formula for the amount of heat stabilizer added)
Methacrylic monomer, mass ratio of component (B): using methacrylic monomer / (B), 0.053 × [(methacrylic ester monomer unit content) / (B)]-0 .4 was calculated and shown in Tables 2-5.
In Examples 1 to 15 and Comparative Examples 1 to 7 in Tables 2 to 4, the methacrylic monomer is the component (A) described above, and Examples 16 to 24 in Table 5 are comparative examples. In 8, 9, the methacrylic monomer is the sum of the component (A) described above and the methacrylic monomer (A ′) used in Production Examples 1 to 3 described later.
The above formula can be used to calculate the amount of heat stabilizer necessary to obtain a sufficiently good thermal stability for practical use. In the table, “<0” indicates that “thermal stability” It can be considered that "necessary amount of agent = 0 parts by mass".

[Measurement method]
(I. Molecular weight measurement of methacrylic resin)
The weight average molecular weight of the methacrylic resin was measured with the following apparatus and conditions.
Measuring apparatus: Gel permeation chromatography (HLC-8320GPC) manufactured by Tosoh Corporation Column: One TSKguardcolumn SuperH-H, two TSKgel SuperHM-M, and one TSKgel SuperH2500 were connected in series in this order.
In this column, the high molecular weight elutes early and the low molecular weight elutes slowly.
Detector: RI (differential refraction) detector Detection sensitivity: 3.0 mV / min
Column temperature: 40 ° C
Sample: 0.02 g of methacrylic resin in 20 mL of tetrahydrofuran Injection amount: 10 μL
Developing solvent: Tetrahydrofuran, flow rate; 0.6 mL / min
As an internal standard, 0.1 g / L of 2,6-di-t-butyl-4-methylphenol (BHT) was added.
The following 10 polymethyl methacrylates (manufactured by Polymer Laboratories; PMMA Calibration Kit M-M-10) having different molecular weights and known monodisperse weight peak molecular weights were used as standard samples for calibration curves.
Weight peak molecular weight (Mp)
Standard sample 1 1,916,000
Standard sample 2 625,500
Standard sample 3 298,900
Standard sample 4 138,600
Standard sample 5 60,150
Standard sample 6 27,600
Standard sample 7 10,290
Standard sample 85,000
Standard sample 9 2,810
Standard document 10 850
Under the above conditions, the RI detection intensity with respect to the elution time of the methacrylic resin was measured.
The weight average molecular weight (Mw) of the methacrylic resin was determined based on the area area in the GPC elution curve and a calibration curve of a seventh-order approximation.

(II. Measurement of residual monomer amount)
The amount of residual monomer contained in the methacrylic resin was measured under the following conditions and equipment.
Sample: <1. Heat resistance; measurement of VICAT softening temperature> The 4 mm-thick test piece produced in the above was cut to obtain a sample for measuring the residual monomer amount.
Measuring device: GC-1700 manufactured by Shimadzu Corporation
Column used: TC-1 φ0.32mm × 30m × 0.25μm
Carrier gas: Nitrogen (1.3mL / min)
Split ratio: (1: 5)
Linear velocity: 23 cm / sec
Column pressure 42 kPa
Total flow rate 11mL / min
Injection volume 0.8μL
Set temperature INJ / DET = 230 ℃ / 300 ℃
Temperature increase program 45 ° C. (held for 5 minutes) → Temperature increased to 90 ° C. at 10 ° C./min. → The temperature was raised to 190 ° C at 30 ° C / min. → The temperature was raised to 220 ° C at 10 ° C / min. → The temperature was raised to 300 ° C at 50 ° C / min.
The residual monomer amount was calculated using a calibration curve prepared in advance for the monomer species to be measured.
In the following table, the residual monomer amount represents the total residual amount of the monomer species subjected to polymerization, and the residual MI monomer amount represents the total residual amount of the maleimide monomer used as the component (B).

(III. Measurement of average particle diameter of rubbery polymer)
The emulsion of rubber-containing copolymer particles was sampled, diluted with water to a solid content of 500 ppm, and the absorbance at a wavelength of 550 nm was measured using a UV1200V spectrophotometer (manufactured by Shimadzu Corporation). .
From this measured value, the average particle size was determined using a calibration curve prepared by measuring the absorbance in the same manner for a sample whose particle size was measured from a transmission electron micrograph.

(IV. Physical property measurement)
<1. Heat resistance; measurement of VICAT softening temperature>
In accordance with ISO 306 B50, measurement was performed using a 4 mm-thick test piece to obtain a VICAT softening temperature (° C.), which was used as an index for heat resistance evaluation.

<2. Transparency; Measurement of total light transmittance>
Based on the ISO 13468-1 standard, the total light transmittance was measured using a 3 mm-thick test piece, and used as an index of transparency.

<3. Moist heat resistance test>
Using a IS-100EN injection molding machine manufactured by Toshiba Machine Co., Ltd., a test piece having a thickness of 3 mm, a width of 100 mm and a length of 100 mm was produced at a molding temperature of 270 ° C. and a mold temperature of 60 ° C., and a temperature of 70 ° C. and a humidity of 95 The shape of the test piece after being left in a constant temperature and humidity chamber set at% for 500 hours was observed and evaluated according to the following criteria.
Deformation such as distortion: “×”
Slightly deformed: “△”
Almost no deformation: “○”

<4. Moldability 1: Fluidity during molding>
Using an IS-100EN injection molding machine manufactured by Toshiba Machine Co., Ltd., a molding temperature of 250 ° C., a mold temperature of 60 ° C., an injection pressure of 56 MPa, an injection time of 20 seconds, and a cooling time of 40 seconds, a thickness of about 3.2 mm × width A test piece of about 12.7 mm × length of about 127 mm was manufactured by injection molding and evaluated according to the following criteria.
Samples obtained: "○"
Short shot due to poor fluidity: “×”

<5. Moldability 2: Presence or absence of silver and presence or absence of cracks during release>
Using a sample dried for 8 hours in a steam oven set at 85 ° C., using IS-100EN injection molding machine manufactured by Toshiba Machine Co., Ltd., at a molding temperature of 290 ° C., a mold temperature of 60 ° C., and a thickness of 3 mm X 100 mm wide x 100 mm long test specimens were manufactured continuously for 50 shots and evaluated according to the following criteria.
(With or without silver)
10 or more specimens with silver observed: “×”
2 to 9 specimens with silver observed: “○”
Silver is observed in 1 sample or less: “◎”
(Presence or absence of cracks during mold release)
When the molded piece was cracked during mold release: “×”
No cracking: “○”

<6. Thermal stability evaluation>
(1% weight loss temperature)
Measurement was carried out under the following apparatus and conditions, and the temperature when the weight decreased by 1% was calculated and used as the thermal decomposition start temperature.
Measuring apparatus: differential type differential thermal balance Thermo plus EVO II TG8120 (manufactured by Rigaku Corporation)
Sample preparation: <4. Formability 1: Flowability at the time of molding> Similar to the method for producing a test piece, a test piece having a thickness of about 3 mm, a width of about 40 mm, and a length of about 60 mm is manufactured and the test piece is cut. The following measurement sample of about 10 mg was obtained.
Sample amount: about 10mg
Measurement atmosphere: Nitrogen (100 mL / min)
Measurement conditions: held at 100 ° C./5 min. → The temperature was raised to 400 ° C. at 10 ° C./min, and the point at which 1% weight was reduced was observed to obtain the thermal decomposition starting temperature (1% weight reduction temperature).
(Decomposition amount at 270 ° C / 30 minutes holding)
Moreover, the measurement was performed under the following setting conditions, and the weight reduction ratio when held at about 270 ° C. for 30 minutes was calculated.
Measuring apparatus: differential type differential thermal balance Thermo plus EVO II TG8120 (manufactured by Rigaku Corporation)
Sample amount: about 10mg
Measurement atmosphere: Nitrogen (100 mL / min)
The temperature was maintained at 50 ° C./2 min. → The temperature was raised to 200 ° C at 20 ° C / min. → The temperature was raised to 250 ° C at 20 ° C / min. → The temperature was raised to a set temperature of 265 ° C. at 10 ° C./min, held for 60 minutes, and the weight loss rate after 30 minutes from the start of the holding was calculated. The measurement temperature was about 270 ° C. at the set temperature of 265 ° C.

<7. Measurement of pencil hardness>
Using an IS-75S injection molding machine manufactured by Toshiba Machine Co., Ltd., a test piece having a thickness of about 3 mm, a width of about 40 mm, and a length of about 60 mm was produced at a molding temperature of 270 ° C. and a mold temperature of 60 ° C. After drying in an oven for 10 hours, measurement was performed in accordance with the conditions of JIS-K-5600-5-4.

<8. Impact resistance evaluation-Charpy impact strength (no notch)>
Measurement was performed in accordance with the ISO 179 / 1eU standard, and evaluation was performed according to the following criteria.
"◎": 25kJ / m ² greater than or equal to "〇": 20kJ / m ² more than 25kJ / m less than ² "△": 15kJ / m ² more than 20kJ / m less than ² "×": 15kJ / m less than ²

<9. Overall evaluation>
In the above evaluation, “◯” indicates that it was determined to be suitable for the visor application, and “X” indicates that a defect was found in any of them and was determined to be inappropriate for the visor application.

Hereinafter, the manufacturing method of methacrylic resin (I) is shown.
The raw materials and blending amounts are shown in Table 1 below.
Moreover, the preparation composition of a monomer, the kind and compounding quantity of a heat stabilizer are shown in the following Tables 2-4.

[Example 1]
2 kg of water, 65 g of tricalcium phosphate, 39 g of calcium carbonate, and 0.39 g of sodium lauryl sulfate were charged into a container having a stirrer equipped with four inclined paddle blades to obtain a mixed solution (a).
Next, 26 kg of water was charged into a 60 L reactor equipped with a stirrer equipped with three blades and the temperature was raised to 40 ° C., and the mixture (a) and the blending amount shown in Table 1 below were shown in Table 2. Raw materials for methacrylic resin were added at a blending ratio.
Next, the temperature was raised to 75 ° C. at a rate of about 1 ° C./min, suspension polymerization was carried out while maintaining about 75 ° C., and an exothermic peak was observed about 150 minutes after the starting material mixture was charged.
Thereafter, the temperature was raised to about 96 ° C. at a rate of about 1 ° C./min, and then aged for 120 minutes to substantially complete the polymerization reaction.
Next, in order to cool to 50 ° C. and dissolve the suspending agent, 20 mass% sulfuric acid was added.
Next, the polymerization reaction solution is passed through a 1.68 mm mesh sieve to remove aggregates, the water is filtered off, the resulting slurry is dehydrated to obtain a bead polymer, and the resulting bead polymer is After washing with water, it was dehydrated in the same manner as described above, and further washed with ion-exchanged water and repeated dehydration to obtain polymer particles.
The obtained polymer particles and the heat stabilizer (E-1) were blended in the amounts shown in Table 2 below, and an ultraviolet absorber JF77 (manufactured by Johoku Chemical Co., Ltd.) was blended at 300 ppm with respect to the resin content. Then, the mixture was melt-kneaded in a twin screw extruder of φ30 mm set at 240 ° C., and the strand was cooled and cut to obtain resin pellets. It was confirmed that the extrusion workability at that time was good.
Using the obtained pellets, an injection molded article was obtained, and the above physical properties were evaluated. The evaluation results are shown in Table 2 below.

[Examples 2 to 12, 14, 15 and Comparative Examples 1 to 6]
Polymerization was performed using the raw materials shown in Table 1 below in the same manner as in Example 1 to obtain polymer particles.
The obtained polymer particles and the component (E) are blended in the types and amounts shown in Tables 2 to 4 below, melt-kneaded in a φ30 mm twin screw extruder set at 240 ° C., and the strand is cooled and cut. Thus, resin pellets were obtained. It was confirmed that the extrusion workability at that time was good.
Moreover, the physical property measurement result of the molded object of the methacrylic resin of Examples 2-14 and 15 and Comparative Examples 1-6 is shown in the following Table 2-Table 4.

Example 13
2 kg of water, 65 g of tricalcium phosphate, 39 g of calcium carbonate, and 0.39 g of sodium lauryl sulfate were charged into a container having a stirrer equipped with four inclined paddle blades to obtain a mixed solution (a).
Next, 26 kg of water was charged into a 60 L reactor equipped with a stirrer equipped with three reciprocating blades, the temperature was raised to 75 ° C., and the mixture (a) and the blending amount shown in Table 1 below are shown in Table 3. Raw materials for methacrylic resin were added at a blending ratio.
Next, suspension polymerization was carried out while maintaining the temperature at about 75 ° C., and an exothermic peak was observed about 130 minutes after the starting material mixture was charged.
Thereafter, the temperature was raised to about 92 ° C. at a rate of about 1 ° C./min, followed by aging for 120 minutes to substantially complete the polymerization reaction.
Next, in order to cool to 50 ° C. and dissolve the suspending agent, 20 mass% sulfuric acid was added.
Next, the polymerization reaction solution is passed through a 1.68 mm mesh sieve to remove aggregates, the water is filtered off, the resulting slurry is dehydrated to obtain a bead polymer, and the obtained bead polymer is After washing with water, it was dehydrated in the same manner as described above, and further washed with ion-exchanged water and repeatedly dehydrated to obtain polymer particles.
The obtained polymer particles and the heat stabilizers (E-1) and (E-3) were blended in the amounts shown in Table 3 below, further blended, into a φ30 mm twin screw extruder set at 240 ° C. The mixture was melt-kneaded, and the strand was cooled and cut to obtain resin pellets. It was confirmed that the extrusion workability at that time was good.
Using the obtained pellets, an injection molded article was obtained, and the above physical properties were evaluated. The evaluation results are shown in Table 3 below.

[Comparative Example 7]
Using a vessel equipped with a stirrer, 78 parts by mass of methyl methacrylate, 14 parts by mass of styrene, 8 parts by mass of maleic anhydride, 0.03 parts by mass of lauroyl peroxide and 0.23 parts by mass of n-octyl mercaptan The parts were mixed and dissolved to prepare a monomer compounding solution.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm are used, and the vicinity of the outer periphery is bonded with a flexible vinyl chloride gasket, and the distance between the two glass plates is 3.5 mm. A cell was prepared and prepared.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the reduced pressure was released and the pressure was returned to normal pressure, and immediately filled into the glass cell.
Next, it is kept in a hot water tank adjusted to 60 to 65 ° C. for 22 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. A sheet-like resin was obtained.
The sheet-like resin obtained as described above was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd. equipped with a 10 mm mesh net, and then the pulverized product was passed through a 500 μm sieve, Fine powder was removed to obtain a pulverized composition.
The recovery rate of the pulverized composition was 93.2%.
The obtained pulverized composition, 0.2 part by mass of (E-1) and 0.4 part by mass of (E-5) were blended and melted in a twin screw extruder of φ30 mm set at 240 ° C. After kneading, the strand was cooled and cut to obtain resin pellets.
It was confirmed that the extrusion workability at that time was good.
Using the obtained pellets, an injection-molded body was produced, and the above physical properties were evaluated. The evaluation results are shown in Table 4 below.

  In Examples 1-15, it had sufficient heat resistance, transparency required as a visor, moist heat resistance were also good, and moldability was also excellent.

[Alloy resin]
A combination of the methacrylic resin (I) produced in Examples 1, 4, 6, and 7 described above and the methacrylic resin (II) produced by <Production Example 1> to <Production Example 3> described later. And the physical properties were evaluated in the same manner as in Example 1 above.
(Manufacture of resin for alloy)
<Production Example 1>
2 kg of water, 65 g of tricalcium phosphate, 39 g of calcium carbonate, and 0.39 g of sodium lauryl sulfate were charged into a container having a stirrer equipped with four inclined paddle blades to obtain a mixed solution (A).
Next, 26 kg of water was charged into a 60 L reactor, the temperature was raised to 80 ° C., the mixed solution (A) was charged, 5700 g of methyl methacrylate (A ′), 30 g of lauroyl peroxide, 2-ethylhexylthioglycolate. Polymer raw material (I) mixed with 122 g was charged.
Thereafter, suspension polymerization was carried out while maintaining the temperature at about 80 ° C. An exothermic peak was observed 100 minutes after adding the polymer raw material (I).
Thereafter, the temperature was raised to 92 ° C. at a rate of 1 ° C./min, and then maintained at about 92 ° C. for 30 minutes.
Thereafter, after the temperature was lowered to 80 ° C. at a rate of 1 ° C./min, polymer raw material (II) in which 17300 g of methyl methacrylate (A ′), 440 g of methyl acrylate, 24 g of lauroyl peroxide, and 29 g of n-octyl mercaptan were mixed. Then, it was put into the reactor, and then suspension polymerization was carried out while maintaining the temperature at about 80 ° C. An exothermic peak was observed 120 minutes after the introduction of the polymer raw material (II).
Thereafter, the temperature was raised to 92 ° C. at a rate of 1 ° C./min and then aged for 60 minutes to substantially complete the polymerization reaction.
Next, in order to cool to 50 ° C. and dissolve the suspending agent, 20 mass% sulfuric acid was added.
Next, the polymerization reaction solution is passed through a 1.68 mm mesh sieve to remove aggregates, the water is filtered off, the resulting slurry is dehydrated to obtain a bead polymer, and the resulting bead polymer is After washing with an aqueous sodium hydroxide solution adjusted to a pH of about 8 to 9.5, it was dehydrated in the same manner as described above, and further washed with ion-exchanged water and repeatedly dehydrated to obtain polymer particles.
The polymer had a weight average molecular weight measured by GPC of 100,000 and a Vicat softening temperature of 109 ° C.

<Production Example 2>
2 kg of water, 65 g of tricalcium phosphate, 39 g of calcium carbonate, and 0.39 g of sodium lauryl sulfate were charged into a container having a stirrer equipped with four inclined paddle blades to obtain a mixed solution (A).
Next, 26 kg of water was charged into a 60 L reactor, the temperature was raised to 80 ° C., the mixture (A) was added, and 21900 g of methyl methacrylate (A ′), 560 g of methyl acrylate, 45 g of lauroyl peroxide and A polymer raw material in which 54 g of n-octyl mercaptan was previously mixed was charged.
Thereafter, suspension polymerization was carried out while maintaining the temperature at about 80 ° C. An exothermic peak was observed 120 minutes after the introduction of the polymer raw material.
Thereafter, the temperature was raised to 92 ° C. at a rate of 1 ° C./min, and then maintained at a temperature of about 92 ° C. for 60 minutes to substantially complete the polymerization reaction.
Next, in order to cool to 50 ° C. and dissolve the suspending agent, 20 mass% sulfuric acid was added.
Next, the polymerization reaction solution is passed through a 1.68 mm mesh sieve to remove aggregates, the water is filtered off, the resulting slurry is dehydrated to obtain a bead polymer, and the resulting bead polymer is After washing with an aqueous sodium hydroxide solution adjusted to a pH of about 8 to 9.5, it was dehydrated in the same manner as described above, and further washed with ion-exchanged water and repeatedly dehydrated to obtain polymer particles.
The polymer had a weight average molecular weight measured by GPC of 100,000 and a Vicat softening temperature of 109 ° C.

<Production Example 3>
Using a vessel equipped with a stirrer, 78 parts by mass of methyl methacrylate (A ′), 14 parts by mass of styrene, 8 parts by mass of maleic anhydride, 0.03 parts by mass of lauroyl peroxide and 0-n-octyl mercaptan .23 parts by mass was mixed and dissolved to prepare a monomer mixture.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm are used, and the vicinity of the outer periphery is bonded with a flexible vinyl chloride gasket, and the distance between the two glass plates is 3.5 mm. A cell was prepared and prepared.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the reduced pressure was released to restore the normal pressure, and the glass cell was immediately poured to fill.
Next, it is kept in a hot water tank adjusted to 60 to 65 ° C. for 22 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. A sheet-like resin was obtained.
The sheet-like resin obtained as described above was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd. equipped with a 10 mm mesh net, and then the pulverized product was passed through a 500 μm sieve, Fine powder was removed to obtain a pulverized product.
The amount of methyl methacrylate (A ′) in the pulverized product is NMR measurement data of a product obtained by dissolving the obtained resin in acetone, reprecipitating from methanol to remove residual monomers, and drying. Based on the above calculation.

[Examples 16 to 22], [Comparative Examples 8 and 9]
Using the polymer particles obtained in Production Example 1, Production Example 2 and Examples 1, 4, 6, and 7, and the pulverized product obtained in Production Example 3, and further, predetermined materials at the blending ratios shown in Table 5 below Blending was performed, and melt-kneading was performed using a φ30 mm twin screw extruder set at 240 ° C., and the strand was cooled and cut to obtain resin pellets.
Using the obtained pellets, an injection-molded body was produced, and the above physical properties were evaluated. The evaluation results are shown in Table 5 below.

  As shown in Table 5 below, Examples 16 to 22 had sufficient heat resistance, good transparency and moist heat resistance required as a visor, and excellent moldability.

[Rubber polymer (III)]
By the methacrylic resin (I) produced in Examples 1 and 6 described above, the methacrylic resin (II) produced by (Production Example 1) described above, and <Production Example 4> to <Production Example 6> described later. A resin composition was produced by combining the produced rubbery polymer (III), and the physical properties were evaluated in the same manner as in Example 1.

The abbreviations shown in the method for producing rubbery polymer (III) to be described later indicate the following compounds.
MMA: methyl methacrylate BA: n-butyl acrylate St: styrene MA: methyl acrylate ALMA: allyl methacrylate PEGDA: polyethylene glycol diacrylate (molecular weight 200)
DPBHP: Diisopropylbenzene hydroperoxide n-OM: n-octyl mercaptan HMBT: 2- (2′-hydroxy-5′-methylphenyl) benzotriazole

<Production Example 4>
(Rubber polymer having a three-layer structure (III-1))
A reactor with an internal volume of 10 L equipped with a reflux condenser was charged with 4600 mL of ion-exchanged water and 24 g of sodium dioctylsulfosuccinate as an emulsifier, and the temperature was raised to 80 ° C. in a nitrogen atmosphere while stirring at a rotational speed of 250 rpm. Was virtually absent (substantially oxygen-free).
Next, Rongalite l. 2 g was added and dissolved uniformly.
As a first layer, a monomer mixture of MMA 150 g, BA 2.5 g, St 40 g, ALMA 0.2 g, and DPBHP 0.2 g was added and polymerized at 80 ° C. The reaction was complete in about 15 minutes.
Next, as a second layer, a monomer mixture of BA 1110 g, St572 g, PEGDA 40 g, ALMA 7.0 g, DPBHP 3.5 g and Rongalite 2.0 g was added dropwise over 90 minutes. The reaction was completed 60 minutes after the completion of the dropwise addition.
Next, a monomer mixture of 190 g of MMA, 2.0 g of BA, 0.2 g of DPBHP, and 0.1 g of n-OM was dropped over 5 minutes as the third layer, and after completion of the dropping, the reaction at this stage was completed in about 15 minutes. .
Finally, a monomer mixture of MMA 380 g, BA 2.5 g, DPBHP 0.4 g, and n-OM 1.2 g was added as the third layer two steps over 10 minutes. This step was complete in about 15 minutes.
The temperature is raised to 95 ° C. and held for 1 hour, and the resulting emulsion is poured into a 0.5% aluminum chloride aqueous solution to agglomerate the polymer, washed 5 times with warm water, dried and dried in a white floc form. Obtained material.
The first layer corresponds to the innermost layer, the second layer corresponds to the intermediate layer, and the third layer corresponds to the outermost layer.
The rubbery polymer (III-1) obtained had an average particle size of 0.1 μm.

<Production Example 5>
(Rubber polymer having a three-layer structure (III-2))
Ion exchange water 4600mL and sodium dioctylsulfosuccinate 33g are put into a reactor with a reflux condenser with an internal volume of 10L, and the temperature is raised to 80 ° C under a nitrogen atmosphere while stirring at a rotational speed of 250 rpm. It was in a state where there was no top (substantially oxygen-free state).
Five minutes after adding 1.0 g of sodium formaldehyde sulfoxylate, 30% by mass of a monomer mixture consisting of MMA 220 g, BA 3.5 g, St 48 g, ALMA 0.27 g and DPBHP 0.27 g was added all at once. The remaining 70% by mass was continuously added over 20 minutes, and after completion of the addition, the mixture was further maintained for 60 minutes to complete the polymerization of the innermost layer.
Next, 5 minutes after adding 0.8 g of sodium formaldehyde sulfoxylate, a monomer mixture consisting of BA620 g, St325 g, ALMA 14 g, tetraethylene glycol diacrylate 4.8 g and DPBHP 2.0 g was continuously added over 60 minutes. After completion of the addition, the mixture was held for another 80 minutes to complete the polymerization of the soft layer (intermediate layer).
Next, a monomer mixture composed of MMA 760 g, BA 50 g, DPBHP 1.6 g and n-OM 1.0 g was continuously added over 70 minutes, and the mixture was held for 60 minutes after the addition was completed.
Next, the temperature was raised to 95 ° C. and held for 60 minutes to complete the polymerization of the outermost layer.
A small amount of the polymer emulsion thus obtained was collected, and the average particle size was determined by the method (2) in the method for measuring physical properties, and found to be 0.09 μm.
The remaining emulsion was poured into a 3% by weight aqueous solution of sodium sulfate, salted out and coagulated, and then repeatedly subjected to dehydration and washing, followed by drying treatment to obtain rubber polymer (III-2). Obtained as a powder.

<Production Example 6>
(Rubber polymer having a three-layer structure)
Ion exchange water 5600mL and sodium dioctylsulfosuccinate 40g were put into a reactor with a reflux condenser with an internal volume of 10L, and the temperature was raised to 80 ° C under a nitrogen atmosphere while stirring at 250 rpm. It was in a state where there was no top (substantially oxygen-free state).
5 minutes after adding 1.2 g of sodium formaldehyde sulfoxylate, 30% by mass of a monomer mixture consisting of 260 g of MMA, 4.2 g of BA, St64 g, 0.33 g of ALMA and 0.33 g of DPBHP was added all at once. The remaining 70% by mass was continuously added over 20 minutes, and after completion of the addition, the mixture was further maintained for 60 minutes to complete the polymerization of the innermost layer.
Next, 5 minutes after adding 1.0 g of sodium formaldehyde sulfoxylate, a monomer mixture consisting of 917 g of BA, St 480 g of St, ALMA 21 g, 7.0 g of tetraethylene glycol diacrylate and 2.9 g of DPBHP was added over 90 minutes. The mixture was continuously added and maintained for 80 minutes after the addition was completed to complete the polymerization of the soft layer (intermediate layer).
Next, a monomer mixture composed of MMA 695 g, BA 45 g, DPBHP 1.47 g and n-OM 0.9 g was continuously added over 60 minutes, and the mixture was held for 60 minutes after the addition was completed.
Next, the temperature was raised to 95 ° C. and held for 60 minutes to complete the polymerization of the outermost layer.
A small amount of the polymer emulsion thus obtained was collected and the average particle size was determined by the absorbance method and found to be 0.08 μm.
The remaining emulsion was put into a 3% by mass sodium sulfate warm aqueous solution, salted out and coagulated, and then dried after repeated dehydration and washing to obtain a rubbery polymer (III-3) as a powder. .

[Examples 23 to 25]
Using the rubbery polymers obtained in Production Examples 4 to 6, melt-kneading was performed in a φ30 mm twin screw extruder in the same manner as in Examples 16 to 22, and the strands were cooled and cut to obtain resin pellets.
Using the obtained pellets, an injection-molded body was produced, and the above physical properties were evaluated. The evaluation results are shown in Table 5 below.

  As shown in Table 5 below, Examples 23 to 25 had sufficient heat resistance, good transparency and moist heat resistance required as a visor, and excellent moldability.

  The present invention has industrial applicability as visors such as side window visors and weather guards.

Claims (15)

Methacrylic acid ester monomer unit (A): 50 to 97% by mass;
At least one structural unit (B) selected from the group consisting of a maleimide structural unit, a glutaric anhydride structural unit, a glutarimide structural unit, and a lactone ring structural unit (B) having a ring structure in the main chain: 3 to 30 masses %When,
0-20% by mass of other vinyl monomer units (C) copolymerizable with the methacrylic acid ester monomer,
Containing,
A visor containing a methacrylic resin (I) having a weight average molecular weight of 650,000 to 300,000 as measured by gel permeation chromatography (GPC). 10 to 99% by mass of the methacrylic resin (I),
Methacrylic resin (II) containing at least 80 to 99.5% by mass of a methacrylic acid ester monomer unit (A ′) and having a weight average molecular weight of 20,000 to 300,000 as measured by gel permeation chromatography (GPC) 90-1% by mass,
The visor of claim 1, further comprising:   The visor according to claim 2, wherein the methacrylic resin obtained by mixing the methacrylic resin (I) and the methacrylic resin (II) has a weight average molecular weight of 650,000 to 300,000.   The visor according to any one of claims 1 to 3, further comprising 1 to 100 parts by mass of a rubbery polymer (III) with respect to 100 parts by mass of the resin component containing the methacrylic resin (I). The structural unit (B) having a ring structure in the main chain,
The visor according to any one of claims 1 to 4, comprising at least one structural unit selected from the group consisting of a glutarimide structural unit, a lactone ring structural unit, and a maleimide structural unit. The structural unit (B) having a ring structure in the main chain,
The visor according to any one of claims 1 to 5, comprising a maleimide-based structural unit. The structural unit (B) having a ring structure in the main chain,
The visor according to any one of claims 1 to 6, comprising an N-cyclohexylmaleimide-based structural unit and / or an N-aryl group-substituted maleimide-based structural unit. The structural unit (B) having a ring structure in the main chain,
The visor according to any one of claims 1 to 7, comprising an N-aryl group-substituted maleimide-based structural unit.   The visor according to any one of claims 1 to 8, further comprising 0 to 5 parts by mass of a heat stabilizer with respect to 100 parts by mass of the methacrylic resin. The visor according to claim 9, wherein the content ratio Y (parts by mass) of the heat stabilizer satisfies the following formula (i) with respect to 100 parts by mass of the methacrylic resin.
(Y) ≧ 0.053 × [methacrylic acid ester monomer unit content / (B) content] −0.4 (i)   The visor according to claim 9 or 10, wherein the heat stabilizer is at least one selected from the group consisting of a hindered phenol-based antioxidant and a phosphorus-based antioxidant.   The other vinyl monomer unit (C) copolymerizable with the methacrylic acid ester monomer is composed of an acrylate monomer, an aromatic vinyl monomer, and a vinyl cyanide monomer. The visor according to any one of claims 1 to 11, wherein the visor is formed of at least one selected from the above.   Other vinyl monomer units (C) copolymerizable with the methacrylic acid ester monomer are formed of at least one selected from the group consisting of methyl acrylate, ethyl acrylate, styrene, and acrylonitrile. The visor according to any one of claims 1 to 12.   The visor according to any one of claims 1 to 13, wherein the Vicat softening temperature is 110 ° C or higher.   The visor according to any one of claims 1 to 14, which has a thickness of 0.1 to 5 mm.