JP5184162B2 - Acrylic resin laminate - Google Patents

Description

  The present invention relates to an acrylic resin laminate, and more specifically, comprises a layer of metal and / or metal oxide on at least one surface of an acrylic resin molded body, and has surface hardness, surface smoothness, and specular gloss. In addition, the present invention relates to an acrylic resin laminate having a metallic luster that is excellent in handleability.

  For the purpose of imparting design properties such as metallic tone to substrates such as automobile interiors, home appliance exteriors, and wallpaper, and protecting the substrates (providing scratch resistance and weather resistance) Resin laminates coated with metal or metal oxide films, particularly metallized laminate films, are used. Among them, acrylic resin laminates, in particular acrylic resin laminate films, are excellent in weather resistance and surface hardness, and are used as decorative materials having a protective function for base materials.

  A molded body consisting only of a methacrylic resin, particularly a film, is not only very brittle and difficult to form a film, but also has a very poor handling property, when trimming at the same time as film formation, when cutting the film after film formation, When the film is bonded to the base material, or when the unnecessary portion (burr) is removed after the film is bonded to the base material, problems such as cracking may occur.

Therefore, in order to improve the brittleness of a molded body made of only this methacrylic resin, an acrylic resin molded body blended with so-called core-shell type particles has been proposed.
For example, Patent Document 1 discloses a core-shell type particle (common name: two-layer type core) obtained by copolymerizing a methacrylic acid alkyl ester and an acrylic acid alkyl ester in the presence of crosslinked particles of an acrylic acid alkyl ester polymer. A film-like or sheet-like molded body obtained by blending shell-type particles) with a methacrylic resin has been proposed.
Japanese Examined Patent Publication No. 56-27378

Since the acrylic resin molded body obtained by blending the two-layer core-shell particles generally has a low surface hardness, the so-called three-layer core-shell particles (Patent Document 2) are used for the improvement. An acrylic resin molded body blended therewith (Patent Documents 3 and 4) has been proposed.
When the surface hardness of the acrylic resin molded body is increased, the scratch resistance is improved, which is advantageous as a protective film.
Japanese Patent Publication No.55-27576 Japanese Patent No. 3287255 Japanese Patent No. 3287315

  By the way, since the core-shell type particles themselves are crosslinked, they do not have fluidity. Therefore, when the core-shell type particles are blended with a methacrylic resin, a part of the core-shell type particles is formed from the surface of the film formed through a film forming process (for example, melt molding or inflation molding using a T die). It was inevitable that the protrusion protruded, which reduced the surface smoothness of the acrylic resin film.

  In particular, the three-layer type core-shell type particles are generally harder to be deformed than the two-layer type core-shell type particles, so that the acrylic resin molded body using the three-layer type core-shell type particles is 2 Although the surface hardness is higher than that using layer-type core-shell type particles, the surface smoothness is significantly reduced.

Deterioration of the surface smoothness of the film is caused by cracking of the film when the film is cut after film formation, when the film is bonded to the base material, or when unnecessary portions (burrs) are removed after being bonded to the base material. The tendency to increase ease.
Further, when a layer of a metal and / or metal oxide is formed on the surface of an acrylic resin molded body, particularly a film, the surface smoothness of the molded body has a very important effect. That is, the surface smoothness of the molded body directly affects the surface smoothness of the metal and / or metal oxide layer formed on the surface, and thus affects the handleability of the laminate and the design properties such as specular gloss. .
Furthermore, the surface smoothness of the acrylic resin molded article is low even when other resin surfaces are decorated with an acrylic resin molded article in which a metal and / or metal oxide layer is formed by the simultaneous injection molding method. For this reason, the surface gloss is remarkably reduced.

  Therefore, as a film having high surface smoothness and capable of expressing good design properties even when a metal and / or metal oxide layer is formed on the film, Patent Document 5 discloses an acrylic melt-extruded from a T die. Containing acrylic rubber particles obtained by forming a film containing acrylic rubber particles-containing acrylic resin sandwiched between two mirror rolls at a pressing pressure of 300 N / cm or more, and containing at least one of the acrylic rubber particles. An acrylic resin molded body having a center line average roughness Ra defined by JIS B0601 of 0.01 to 0.05 μm has been proposed.

In Patent Document 5, Ra is measured with a surface roughness meter ["Surfcom 570A type" manufactured by Tokyo Seimitsu Co., Ltd.] using a measuring stylus with a radius of 3 [mu] m. According to the study by the present inventors, the size of this measurement stylus is much larger than that of core-shell type particles (usually several tens to several hundreds of nm), so the degree of protrusion of the core-shell type particles can be accurately determined. It was found that it was not evaluated. Further, it was found that even if there were aggregated core-shell type particles (usually several hundred nm to 1 μm), they were not reflected so much in Ra. Therefore, even in the case of an acrylic resin molded product having a center line average roughness Ra within the above range, after film formation, when the film is bonded to the base material, or after being bonded to the base material When removing unused parts (burrs), it is possible to sufficiently prevent unintended film cracking starting from defects caused by protruding core-shell type particles or aggregated core-shell type particles. There wasn't.
Japanese Patent Laid-Open No. 2003-253016

  An object of the present invention is to provide a metal luster having an excellent surface hardness, surface smoothness, mirror gloss, and excellent handleability, comprising a layer of a metal and / or metal oxide on at least one surface of an acrylic resin molded body. It is providing the acrylic resin laminated body which has.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have determined that a specific glass transition obtained by melt-kneading a specific methacrylic resin and a specific polyvinyl acetal resin at a specific mass ratio. By providing a layer made of a metal or metal oxide on at least one surface of a molded article having temperature, an acrylic resin laminate having excellent surface hardness and handleability, excellent surface smoothness, and excellent metallic luster is obtained. It was found that it can be obtained. The present invention has been further studied and completed based on this finding.

That is, according to the present invention, the degree of acetalization obtained by (co) acetalizing a methacrylic resin [A] having a weight average molecular weight of 40000 or more and a polyvinyl alcohol resin having a number average polymerization degree of 200 to 4000 is 55. -83 mol% polyvinyl acetal resin [B] in a mass ratio ([A] / [B]) 99/1 to 51/49, and the glass transition temperature Tg of the methacrylic resin (A) alone. at least one surface of the acrylic resin molded article has a glass transition temperature Tg _AP due to methacrylic resin (a) between the glass transition temperature Tg _B in the polyvinyl acetal resin (B) alone and _a, metal and / Or the acrylic resin laminated body provided with the layer which consists of metal oxides is provided.

  The acrylic resin laminate of the present invention has excellent surface hardness, surface smoothness, and specular gloss, and is excellent in handleability. The laminate of the present invention can be suitably used for products that require design properties by taking advantage of this feature.

Hereinafter, the present invention will be described in detail.
The acrylic resin laminate of the present invention has a metal and / or metal oxide layer on at least one surface of an acrylic resin molded body containing a methacrylic resin [A] and a polyvinyl acetal resin [B]. It is prepared.

The methacrylic resin [A] used in the present invention can be obtained by polymerizing a monomer mixture containing an alkyl methacrylate.
As alkyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, myristyl Examples thereof include methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, cyclohexyl methacrylate, and phenyl methacrylate. Of these, alkyl methacrylates having 1 to 4 carbon atoms in the alkyl group are preferred, and methyl methacrylate is particularly preferred. These alkyl metallates may be used alone or in combination of two or more.

Examples of monomers other than alkyl methacrylate include alkyl acrylate. Other ethylenically unsaturated monomers that can be copolymerized with alkyl methacrylate and alkyl acrylate are also included.
As alkyl acrylates, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, myristyl Examples include acrylate, palmityl acrylate, stearyl acrylate, behenyl acrylate, cyclohexyl acrylate, and phenyl acrylate. Of these, alkyl acrylates having 1 to 8 carbon atoms in the alkyl group are preferred. These alkyl acrylates may be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer copolymerizable with alkyl methacrylate and alkyl acrylate include diene compounds such as 1,3-butadiene and isoprene; styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, Styrene substituted with halogen, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, etc. Vinyl aromatic compounds; ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, acrylamide, methacrylamide, maleic anhydride, maleic imide, monomethyl maleate, dimethyl maleate, etc. It is possible. These ethylenically unsaturated monomers may be used alone or in combination of two or more.

  In the methacrylic resin [A] used in the present invention, the proportion of the alkyl methacrylate unit is preferably 50 to 100% by mass and more preferably 80 to 99.9% by mass from the viewpoint of weather resistance. .

  Moreover, it is preferable to contain an alkyl acrylate unit in 0.1-20 mass% from a heat resistant viewpoint of methacrylic resin [A].

  The methacrylic resin [A] used in the present invention has a weight average molecular weight (denoted as Mw, the same shall apply hereinafter) of 40,000 or more, preferably 40,000 to 10,000, from the viewpoint of strength characteristics and meltability. 000, more preferably 80,000 to 1,000,000. The methacrylic resin (A) used in the present invention may be one in which monomers are linearly bonded, may have a branch, or may have a cyclic structure. good.

  The methacrylic resin [A] used in the present invention is not particularly limited as long as it is a method capable of polymerizing an α, β-unsaturated compound, but is preferably produced by radical polymerization. Examples of the polymerization method include bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization.

  Examples of radical polymerization initiators used in the polymerization include azo compounds such as azobisisobutyronitrile and azobisγ-dimethylvaleronitrile; benzoyl peroxide, cumyl peroxide, oxyneodecanoate, diisopropyl peroxydicarbonate, t Examples thereof include peroxides such as -butyl cumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and lauroyl peroxide. The polymerization initiator is usually used in an amount of 0.05 to 0.5 parts by mass with respect to 100 parts by mass of all monomers. The polymerization is usually performed at a temperature of 50 to 140 ° C., usually for 2 to 20 hours.

  In order to control the molecular weight of the methacrylic resin [A], a chain transfer agent can be used. Examples of chain transfer agents include methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, t-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, ethylthioglycoate, mercaptoethanol, thio- β-naphthol, thiophenol and the like can be mentioned. A chain transfer agent is normally used in 0.005-0.5 mass% with respect to all the monomers.

  The polyvinyl acetal resin [B] is usually a resin having a repeating unit represented by Chemical Formula 1.

In Chemical Formula 1, n is a number (natural number) indicating the type of aldehyde used in the acetalization, R ₁ , R ₂ ,..., R _n are alkyl residues or hydrogen atoms of the aldehyde used in the acetalization reaction. _{, k (1), k (} 2), ···, k (n) each of R _1, R _2, ···, the proportion of acetal units containing R _n (mol ratio), l is the vinyl alcohol unit The ratio (mol ratio), m is the ratio (mol ratio) of vinyl acetate units. However, k ₍₁₎ + k ₍₂₎ + ... + k _(n) + l + m = 1, and k ₍₁₎ , k ₍₂₎ , ..., k _(n) , l, and m are any May be zero. The repeating units are not particularly limited by the arrangement order shown in Chemical Formula 1, and may be arranged at random, may be arranged in a block shape, or may be arranged in a taper shape.

  The polyvinyl acetal resin [B] used in the present invention can be obtained, for example, by reacting a polyvinyl alcohol resin and an aldehyde.

  The number average polymerization degree of the polyvinyl alcohol resin used for the production of the polyvinyl acetal resin [B] is usually 200 to 4,000, preferably 300 to 3,000, more preferably 500 to 2,000. When the number average polymerization degree of the polyvinyl alcohol resin is less than 200, the mechanical properties of the obtained polyvinyl acetal resin are insufficient, and the mechanical properties, particularly toughness, of the acrylic resin laminate of the present invention tends to be insufficient. On the other hand, when the number average polymerization degree of the polyvinyl alcohol resin exceeds 4,000, the melt viscosity at the time of melt-kneading with the methacrylic resin tends to increase.

A polyvinyl alcohol resin is not specifically limited by the manufacturing method, For example, what was manufactured by saponifying polyvinyl acetate etc. with an alkali, an acid, ammonia water, etc. can be used.
The polyvinyl alcohol resin may be completely saponified, or may be a partially saponified partially saponified polyvinyl alcohol resin. It is preferable to use a saponification degree of 80 mol% or more.

As the polyvinyl alcohol resin, a copolymer of vinyl alcohol and a monomer copolymerizable therewith, such as an ethylene-vinyl alcohol copolymer resin and a partially saponified ethylene-vinyl alcohol copolymer resin, can be used. . Furthermore, a modified polyvinyl alcohol resin into which carboxylic acid or the like is partially introduced can be used.
These polyvinyl alcohol resins may be used individually by 1 type, and may be used in combination of 2 or more types.

  The aldehyde used for the production of the polyvinyl acetal resin [B] is not particularly limited. For example, formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, butyraldehyde, n-octylaldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, glyoxal, Examples include glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde and the like. These aldehydes may be used alone or in combination of two or more. Of these aldehydes, those mainly composed of butyraldehyde are preferred.

The polyvinyl acetal resin [B] obtained by performing acetalization of the polyvinyl alcohol resin with an aldehyde mainly composed of butyraldehyde is particularly called polyvinyl butyral. In this invention, the polyvinyl butyral which the ratio (refer the following formula) of a butyral unit out of the acetal unit which exists in polyvinyl acetal resin [B] exceeds 0.9 is preferable. That is, in the structural formula of the polyvinyl acetal resin shown in Chemical Formula ₁ , when R ₁ = C ₃ H ₇ (alkyl residue of butyraldehyde), k ₍₁₎ / (k ₍₁₎ + k ₍₂₎ + -It is preferable that + k _(n) )> 0.9.

  The reaction between the polyvinyl alcohol resin and the aldehyde ((co) acetalization reaction) can be performed by a known method. For example, an aqueous solution method in which an aqueous solution of a polyvinyl alcohol resin and an aldehyde are acetalized in the presence of an acid catalyst to precipitate resin particles, the polyvinyl alcohol resin is dispersed in an organic solvent, and the aldehyde and the aldehyde are present in the presence of an acid catalyst. Examples thereof include a solvent method in which an acetalization reaction is performed and the reaction solution is precipitated with water or the like which is a poor solvent for the polyvinyl acetal resin. Of these methods, the aqueous medium method is preferable.

  The acid catalyst is not particularly limited. For example, organic acids such as acetic acid and p-toluenesulfonic acid; inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid; gas which shows acidity when an aqueous solution such as carbon dioxide gas is used; cation exchange And solid acid catalysts such as metal oxides and metal oxides.

The degree of acetalization of the polyvinyl acetal resin [B] is 55 to 83 mol%. By using a polyvinyl acetal resin having a degree of acetalization within this range, an acrylic resin molded article used in the present invention can be obtained easily and at low cost by melt processing or production.
In addition, the acetalization degree (mol%) of polyvinyl acetal resin (B) can be defined by the following formula | equation.
Acetalization degree (mol%) =
{K ₍₁₎ + k ₍₂₎ + ... + k _(n) } × 2
/ {{K ₍₁₎ + k ₍₂₎ +... + K _(n) } × 2 + l + m} × 100

The degree of acetalization of the polyvinyl acetal resin is determined by titration of the mass proportion of vinyl alcohol units (l ₀ ) and the proportion of vinyl acetate units (m ₀ ) according to the method described in JIS K6728 (1977). The mass ratio (k ₀ ) of the unit is obtained by k ₀ = 1−l ₀ −m ₀ , and from this, the molar ratio (l) of the vinyl alcohol unit and the molar ratio (m) of the vinyl acetate unit are calculated, and k = 1− The ratio of vinyl acetal units (k = k ₍₁₎ + k ₍₂₎ +... + k _(n) ) is calculated by the formula of 1−m, and the degree of acetalization (mol%) = {k ₍₁₎ + k ₍₂₎ + ... + k _(n) } × 2 / {{k ₍₁₎ + k ₍₂₎ + ... + k _(n) } × 2 + l + m} × 100, or polyvinyl acetal resin Deuterated dimethylsulfur Was dissolved in Okisaido may be calculated by measuring the ¹ H-MMR or ¹³ C-NMR,.

The ratio of acetalization with butyraldehyde is particularly called the degree of butyralization. In the structural formula of polyvinyl acetal shown in Chemical Formula ₁ , when R ₁ = C ₃ H ₇ (an alkyl residue of butyraldehyde), the degree of butyralization is defined by the following formula.
Butyral degree (mol%) = {k ₍₁₎ } × 2
/ {{K ₍₁₎ + k ₍₂₎ +... + K _(n) } × 2 + l + m} × 100

  More preferably, the polyvinyl acetal resin [B] used in the present invention has a butyralization degree of 55 to 75 mol%. When a polyvinyl acetal resin having a butyralization degree in the above range is used, it is excellent in mechanical properties, particularly toughness, and an acrylic resin molded product used in the present invention can be obtained easily and inexpensively. Further, when a polyvinyl acetal resin having a butyralization degree in the above range is used, the difference between the refractive index of the methacrylic resin (A) and the refractive index of the polyvinyl butyral is reduced, and the transparent characteristic of the methacrylic resin (A) is obtained. (High visible light transmittance, low haze) is easily maintained. Furthermore, when stretched, bent, subjected to an impact, and / or placed in a wet and heat condition for a long time, the feature of hardly whitening is likely to appear.

  If the degree of butyralization is less than 55 mol%, the production cost of the polyvinyl acetal resin is high, the thermal stability is lowered, and the yellowness (YI) of the acrylic resin molded product used in the present invention tends to increase. Further, the compatibility with the methacrylic resin is lowered, and the mechanical properties, particularly the toughness, of the acrylic resin laminate of the present invention tends to be lowered, and the handleability tends to be deteriorated. When the degree of butyralization exceeds 75 mol%, the compatibility with the methacrylic resin is lowered, the mechanical properties, particularly the toughness, of the acrylic resin laminate of the present invention tends to be lowered, and the handleability tends to deteriorate. Further, the difference between the refractive index of the methacrylic resin [A] and the refractive index of the polyvinyl acetal resin [B] increases, and the transparency that is a feature of the methacrylic resin [A] tends to decrease.

  Moreover, suitable polyvinyl acetal resin [B] contains 17-45 mol% of vinyl alcohol units normally, and usually contains 0 mol% or more and 5 mol% or less of vinyl acetate units, Preferably it contains 0 mol% or more and 3 mol% or less.

The slurry produced in the aqueous medium method and the solvent method is usually acidic due to an acid catalyst. As a method for removing the acid catalyst, the slurry is repeatedly washed with water, and the pH is usually adjusted to 5 to 9, preferably 6 to 9, more preferably 6 to 8; a neutralizing agent is added to the slurry, The method of adjusting pH to 5-9 normally, Preferably 6-9, More preferably, 6-8; The method of adding alkylene oxides etc. are mentioned.
Examples of the compound used for removing the acid catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, ammonia, sodium acetate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, ammonia, and an aqueous ammonia solution. Examples of alkylene oxides include ethylene oxide, propylene oxide; glycidyl ethers such as ethylene glycol diglycidyl ether.

Next, salts generated by neutralization, aldehyde reaction residues, and the like are removed. The removal method is not particularly limited, and methods such as repeated dehydration and water washing are usually used.
The water-containing polyvinyl acetal resin from which residues and the like have been removed is dried as necessary, and further processed into powder, granules, or pellets as necessary, and used as a molding material. When processing into a powder, granule, or pellet, it is preferable to reduce the reaction residue of aldehyde, moisture, etc. by deaeration in a reduced pressure state.

In the acrylic resin molded body used in the present invention, at least two glass transition temperatures are observed in the dynamic viscoelasticity measurement. One is the glass transition temperature (Tg _AP ) attributed to the methacrylic resin (A), and the other is the glass transition temperature (Tg _BP ) attributed to the polyvinyl acetal resin (B).
When only one glass transition temperature can be observed, that is, when Tg _AP = Tg _BP , the methacrylic resin (A) and the polyvinyl acetal resin (B) in the acrylic resin molding are completely compatible. It is shown that.
When Tg _AP = Tg _A and Tg _BP = Tg _B , this indicates that the methacrylic resin (A) and the polyvinyl acetal resin (B) are in a completely incompatible state.
In contrast, the acrylic resin molded article used in the present invention has a glass transition temperature Tg _AP due to methacrylic resin (A) is a methacrylic resin (A) alone with a glass transition temperature (Tg _A) It is a value between the glass transition temperature (Tg _B ) of the polyvinyl acetal resin (B) alone. That is, the relationship of Tg _B <Tg _AP <Tg _A or Tg _A <Tg _AP <Tg _B is satisfied. It is considered that the acrylic resin molded body having Tg _AP satisfying such a relationship is in a state where the methacrylic resin (A) and the polyvinyl acetal resin (B) are partially compatible. And it is preferable that the acrylic resin molded object used for this invention is what the methacrylic resin (A) comprises the continuous phase at least.
In the present invention, when the methacrylic resin (A) is a combination of two or more methacrylic resins, the glass transition temperature of any one of the combinations is Tg _A , and the polyvinyl acetal resin (B) is In the case of a combination of two or more polyvinyl acetal resins, the glass transition temperature of any one of the combinations is defined as Tg _B , and the above relationship, that is, Tg _B <Tg _AP <Tg _A or Tg _A <Tg _AP It is sufficient if the relationship <Tg _B is satisfied.

Although the detailed reason is not clear, when the methacrylic resin (A) and the polyvinyl acetal resin (B) are partially compatible, the acrylic resin molded body has heat resistance, surface hardness, and rigidity as compared with the methacrylic resin. It is almost the same, and it is difficult to whiten when stretched, bent, subjected to an impact, and / or placed under a wet and heat condition for a long time. In addition, it has excellent toughness and handleability.
On the other hand, when the methacrylic resin (A) and the polyvinyl acetal resin (B) are completely compatible, the surface hardness of the acrylic resin molded product tends to decrease. Further, when the methacrylic resin (A) and the polyvinyl acetal resin (B) are completely compatible and Tg _B <Tg _A , the heat resistance tends to decrease. When the methacrylic resin (A) and the polyvinyl acetal resin (B) are completely incompatible, the strength decreases or whitens.

  In the acrylic resin molded body constituting the present invention, the mass ratio [A] / [B] of the methacrylic resin [A] and the polyvinyl acetal resin [B] is 99/1 to 51/49. From the viewpoint of toughness, that is, handleability and surface hardness of the acrylic resin laminate of the present invention, the mass ratio [A] / [B] is preferably 95/5 to 60/40, and 90/10 to 60 / More preferably, it is 40.

  When the proportion of the polyvinyl acetal resin [B] is less than 1% by mass, mechanical properties such as toughness of the acrylic resin laminate of the present invention tend to be lowered, and the handleability of the laminate tends to be deteriorated. On the other hand, when the proportion of the polyvinyl acetal resin [B] exceeds 49% by mass, the surface hardness of the acrylic resin laminate of the present invention tends to be insufficient.

  The acrylic resin molding used in the present invention has various additives as required, for example, antioxidants, stabilizers, lubricants, processing aids, antistatic agents, antioxidants, colorants, impact resistance. Auxiliaries, foaming agents, fillers, matting agents and the like may be added. In addition, it is preferable not to add a large amount of a softening agent or a plasticizer from the viewpoint of mechanical properties and surface hardness of the acrylic resin laminate of the present invention.

  It is preferable to add an ultraviolet absorber to the acrylic resin molded body used in the present invention for the purpose of improving the weather resistance. Although the kind of ultraviolet absorber is not specifically limited, A benzotriazole type or a triazine type is preferable. The addition amount of the ultraviolet absorber is usually 0.1 to 10% by mass, preferably 0.3 to 5% by mass, based on the total mass of the methacrylic resin [A] and the polyvinyl acetal resin [B]. More preferably, it is 0.3-2 mass%.

  The additive added to the acrylic resin molded body may be added to the methacrylic resin [A] and / or the polyvinyl acetal resin [B] before melt kneading, or the methacrylic resin [A]. And polyvinyl acetal resin [B] may be added when melt-kneading, or when a composition containing methacrylic resin [A] and polyvinyl acetal resin [B] is prepared and the composition is molded It may be added. Alternatively, the methacrylic resin [A], the polyvinyl acetal resin [B], and the above additives may be mixed and directly molded to produce an acrylic resin molded body.

  In the acrylic resin molded body constituting the present invention, the methacrylic resin [A] preferably forms a continuous phase. When the methacrylic resin [A] forms a continuous phase, an acrylic resin laminate having good heat resistance and high surface hardness derived from the methacrylic resin [A] is obtained.

  The acrylic resin molded product used in the present invention is not particularly limited by its production method, but the above-mentioned methacrylic resin [A] and polyvinyl acetal resin [B] are mixed in the above mass ratio ([A] / [B]. It is preferable to obtain it by melt kneading and molding.

In particular, methacrylic resin [A] and polyvinyl acetal resin [B] are melt-kneaded at a resin temperature of 140 ° C. or higher while being sheared at a shear rate of 100 sec ⁻¹ or higher, and then cooled to a temperature of 120 ° C. or lower. It is preferable to further include a step.
In a more preferred production method, when the methacrylic resin (A) and the polyvinyl acetal resin (B) are melt-kneaded at a resin temperature of 140 ° C. or higher, a shearing rate of 100 sec ⁻¹ or higher is applied, It is preferable that the step of setting the speed to 50 sec ⁻¹ or less is performed at least twice. By passing through such a process, an acrylic resin molded body in which at least the methacrylic resin (A) forms a continuous phase can be obtained.

If it is a manufacturing method including the above-mentioned process, once a methacrylic resin [A] and a polyvinyl acetal resin [B] are known kneading machines such as a single screw extruder, a twin screw extruder, a Banbury mixer, a brabender, an open roll, and a kneader. was used to melt-kneaded in the respective constituent shear rate 100 sec ^-1 or more shear applied while the resin temperature 140 ° C. or higher, preferably, applying a shear or shear rate 100 sec ^-1, the shear rate And at least twice each step of 50 sec ^-1 or less, melt kneaded at a resin temperature of 140 ° C or higher, then rapidly cooled to 120 ° C or lower, cut as necessary to form a pellet, and then melt extruded. A molded body may be prepared, or a mixture containing a methacrylic resin [A] and a polyvinyl acetal resin [B] directly. While applying a shear rate 100 sec ^-1 or more shear, preferably, applying a shear or shear rate 100 sec ^-1, through at least 2 times each and the steps to the shear rate 50 sec ^-1 or less, the resin temperature It may be melted at 140 ° C. or higher and rapidly cooled to 120 ° C. or lower to directly produce a molded body such as a film.

  Among these production methods, a large shearing force is obtained, and the methacrylic resin [A] tends to form a continuous phase and is excellent in stability and handleability. Therefore, it is cooled after being melt-kneaded using a twin screw extruder. It is preferable to cut as necessary to once form a pellet, and then melt extrude the pellet to produce a molded body. The resin temperature at the time of melt kneading is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, and particularly preferably 180 ° C. or higher. Moreover, it is preferable that it is 300 degrees C or less from a viewpoint of suppressing deterioration with methacrylic resin [A] and polyvinyl acetal resin [B], and it is further more preferable that it is 280 degrees C or less.

Shear which gives the time of melt-kneading is preferably a shear rate is 100 sec ^-1 or more, and particularly preferably 200 sec ^-1 or more.
When producing pellets of the above mixture, if the resin temperature is melted at 140 ° C. or higher while applying a shear of 100 sec ⁻¹ or higher and cooled to 120 ° C. or lower, 100 sec ⁻¹ or higher is again produced when forming the molded body. Although the resin may be melted at a resin temperature of 140 ° C. or higher while applying the shearing, it is not particularly necessary.

  The acrylic resin molded body used in the present invention can be obtained by selecting an arbitrary molding method according to the shape required for the molded body. When the acrylic resin molded body is a film, it can be molded using a known method such as a T-die method, an inflation method, a melt casting method, or a calendar method. From the viewpoint of obtaining a molded article having good surface smoothness, good specular gloss, and low haze, the molten kneaded product is extruded from a T die in a molten state, and both surfaces thereof are brought into contact with a mirror roll surface or a mirror belt surface. A method including a molding step is preferred. The roll or belt used at this time is preferably made of metal. When both sides of the melt-kneaded product thus extruded are brought into contact with the mirror surface and molded, it is preferable to press and sandwich the both sides of the molded body with a mirror roll or a mirror belt. The pinching pressure by the mirror roll or the mirror belt is preferably high, and the linear pressure is preferably 10 N / mm or more, and more preferably 30 N / mm or more.

  Also, from the viewpoint of obtaining an acrylic resin molded article having good surface smoothness, good mirror gloss, and low haze, the surface temperature of at least one of a mirror roll or a mirror belt sandwiching the acrylic resin molded article is 60 ° C. or higher. In addition, it is preferable that the surface temperature of both the mirror roll or the mirror belt sandwiching the molded body is 130 ° C. or less. When the surface temperature of both the mirror roll or the mirror belt sandwiching the molded product is less than 60 ° C, the surface smoothness and haze of the resulting acrylic resin molded product tend to be insufficient, and at least one surface temperature is 130 ° C. If it exceeds, the molded body and the mirror roll or mirror belt will be in close contact with each other. Therefore, the surface of the molded body will be rough when the acrylic resin molded body is peeled off from the mirror roll or mirror belt, and the surface of the resulting acrylic resin molded body will be smooth. Tend to be low or haze to be high.

  In the acrylic resin molded body, the roughness of at least one surface, specifically, the surface on which the metal and / or metal oxide layer is provided is preferably 1.5 nm or less, more preferably 0.1 to 1.. 0 nm. More preferably, both surfaces of the acrylic resin molded body have a roughness of 1.5 nm or less. When a metal and / or metal oxide layer is provided on the surface having such roughness, the surface roughness of the metal and / or metal oxide layer is reduced, and a laminate having excellent gloss can be obtained. it can. Further, when the metal and / or metal oxide layer is provided, the gloss is excellent even when the thickness of the layer is reduced, which is economical. Furthermore, even when a metal and / or metal oxide layer is provided, there are few cracks when the laminate is cut or punched, and the handleability is excellent. The roughness of the acrylic resin molded product is a value determined by the method described in the examples.

  Further, the haze of the acrylic resin molded body used in the present invention is preferably 0.3% or less, more preferably 0.2% or less, at a thickness of 100 μm. This makes it easy to handle at the time of cutting and punching, etc., and when used for applications that require design, the surface gloss and the sharpness of the pattern layer printed on the acrylic resin molded product Excellent. Further, in optical applications such as a liquid crystal protective film and a light guide film, the use efficiency of the light source is preferably increased. Furthermore, it is preferable because it is excellent in shaping accuracy when performing surface shaping.

  The thickness of the acrylic resin molded product used in the present invention is preferably 500 μm or less. If it is thicker than 500 μm, the secondary processability such as laminating property, handling property, cutting property and punching property tends to decrease and the unit price per unit area also increases, which tends to be economically disadvantageous. In particular, the thickness of the acrylic resin molded body is more preferably 50 to 300 μm, and more preferably 75 to 200 μm.

  The acrylic resin molding used in the present invention may be colored. As a coloring method, a composition of a methacrylic resin [A] and a polyvinyl acetal resin [B] is made to contain a pigment or a dye, and the resin itself before forming a molded body is colored; Examples of the dyeing method include coloring in a liquid in which the dye is dispersed, but the method is not particularly limited thereto.

  The acrylic resin molded body used in the present invention may be printed on at least one surface. Patterns and colors such as pictures, characters and figures are added by printing. The pattern may be chromatic or achromatic. In order to prevent discoloration of the printing layer, printing is preferably performed on the side in contact with other thermoplastic resin and / or thermosetting resin described later.

  The surface of the acrylic resin molded product used in the present invention is JIS pencil hardness (thickness: 100 μm), preferably H or harder than that. Since the acrylic resin molded body having a hard surface is hard to be damaged, it is suitably used as a decorative and protective film for the surface of a molded product requiring a design property.

The acrylic resin molded body used in the present invention may have at least one other thermoplastic resin layer provided on at least one surface thereof, directly or via an adhesive layer.
Other thermoplastic resins suitable for lamination include polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, other (meth) acrylic resins, ABS (acrylonitrile-butadiene- Styrene copolymer) resin and the like.

The method for laminating other thermoplastic resin layers is not particularly limited. For example, (1) Acrylic resin molded body and thermoplastic resin molded body are prepared separately, and a method of laminating continuously between heating rolls, a method of thermocompression bonding with a press, a pressure air or a vacuum molding simultaneously Laminating method, laminating method with an adhesive layer interposed (wet lamination); (2) Laminating another thermoplastic resin melt-extruded from a T-die using an acrylic resin molded body as a base material; (3 ) A method of coextruding a mixture of the aforementioned methacrylic resin [A] and the aforementioned polyvinyl acetal resin [B] with another thermoplastic resin, and the like.
Among these methods, in the method (1) or (2), surface treatment such as corona treatment is applied to the bonding surface side of the acrylic resin molded body or other thermoplastic resin molded body before lamination. May be.

In the laminate of the present invention, a metal and / or metal oxide layer is provided on at least one surface of the acrylic resin molded body.
As the metal, for example, aluminum, silicon, magnesium, palladium, zinc, tin, nickel, silver, copper, gold, indium, stainless steel, chromium, titanium and the like can be used, and as the metal oxide, for example , Aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, silicon oxide, cobalt oxide, zirconium oxide, tin oxide, titanium oxide, iron oxide, copper oxide, Nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, barium oxide, and the like can be used. These metals and metal oxides may be used alone or as a mixture of two or more. Among these, indium is preferable because it has an excellent design and is not easily lost in gloss when the laminate is deep-drawn. Aluminum is particularly preferable when it does not require a deep drawing because it has an excellent design and can be obtained industrially at a low cost. As a method of providing these metal and / or metal oxide layers, a vacuum deposition method is usually used, but a method such as ion plating, sputtering, or CVD (Chemical Vapor Deposition) may be used. . The thickness of the deposited film made of metal and / or metal oxide is generally about 5 to 100 nm. When deep drawing is performed after layer formation, the thickness is preferably 5 to 250 nm.

  The higher the surface smoothness of the acrylic resin molding, the better the adhesion between the metal and / or metal oxide layer and the acrylic resin, and the more difficult it is to peel off at this interface. Furthermore, when the surface smoothness of the acrylic resin molding is high, a laminate having good design properties such as gloss can be obtained even if the thickness of the metal and / or metal oxide layer is reduced. If the surface smoothness is poor, it becomes easier to have a defect that does not have a metallic luster when the thickness of the metal and / or metal oxide layer is reduced, so the roughness of the acrylic resin molded product varies depending on the surface. In some cases, the surface having the lowest roughness (excellent surface smoothness), specifically, the surface having a roughness of preferably 1.5 nm or less, more preferably 0.1 to 1.0 nm, a metal It is preferable to form a metal oxide layer.

  The acrylic resin laminate of the present invention can be made into various structures by being adhered to the surface of other thermoplastic resins and / or thermosetting resins.

  Other thermoplastic resins used in the structure include polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, other (meth) acrylic resins, ABS (acrylonitrile- Butadiene-styrene copolymer) resin. Examples of other thermosetting resins include epoxy resins, phenol resins, and melamine resins.

  The manufacturing method of the structure of the present invention is not particularly limited. For example, the structure of the present invention is obtained by subjecting the acrylic resin laminate of the present invention to the surface of another thermoplastic resin and / or thermosetting resin by vacuum molding, pressure molding, or compression molding under heating. be able to. In the structure of the present invention, the acrylic resin laminate of the present invention is provided on the outermost layer of the structure, thereby being excellent in surface smoothness, surface hardness, gloss, etc., and further in the acrylic resin laminate. The printed pattern is clearly displayed.

When the acrylic resin laminate of the present invention is in the form of a film, a sheet or a plate, it is used as a film, sheet or plate (hereinafter simply referred to as a film) used in the injection molding simultaneous bonding method. Is preferred.
In this injection molding simultaneous bonding method, a film is inserted between male and female molds for injection molding, and a thermoplastic resin melted from one side of the film is injected into the mold to form an injection molded body. In this method, the film is bonded to the molded body. The structure of this invention can be suitably manufactured by the said injection molding simultaneous bonding method.

The film-like acrylic resin laminate of the present invention to be inserted into the mold may be flat, or it is pre-formed by vacuum forming, pressure forming, etc. and shaped into an uneven shape. Also good.
The film-shaped laminate may be preformed separately by a separate molding machine, or may be preformed in a mold of an injection molding machine used for the simultaneous injection molding laminating method. The latter method, that is, a method in which a film-shaped laminate is preformed and then a molten resin is injected on one side thereof is called an insert molding method.

When simultaneously bonding by injection molding, the metal and / or metal oxide layer side of the laminate of the present invention becomes the resin side to be injection-molded, that is, the metal or metal oxide layer is injected with an acrylic resin. It arrange | positions so that it may be pinched | interposed with resin formed by shape | molding.
The structure thus obtained is in a state in which the acrylic resin molded body is disposed on the outermost surface, and is excellent in surface smoothness, surface hardness, gloss, and the like, and also in a sense of depth.

  The laminate of the present invention is an article that requires good design by utilizing good surface smoothness, high surface hardness and good specular gloss, and handleability, that is, an advertising tower, a stand signboard, a sleeve signboard, a billboard signboard, Signboard parts such as roof signboards; display parts such as showcases, partition plates, and store displays; lighting parts such as fluorescent lamp covers, mood lighting covers, lamp shades, light ceilings, light walls, and chandeliers; furniture, pendants, mirrors, etc. Interior parts: Doors, domes, safety window glass, partitions, staircases, balconies, roofs of leisure buildings, etc .; aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus shading boards, automobiles Automatic for side visors, rear visors, head wings, headlight covers, automotive interior parts, bumpers, etc. Transportation equipment-related parts such as exterior members; nameplates for audio and visual images, stereo covers, TV protection masks, electronic equipment parts such as vending machines, mobile phones and personal computers; medical equipment parts such as incubators and X-ray parts; machine covers and instruments Equipment-related parts such as covers, experimental equipment, rulers, dials, observation windows; traffic-related parts such as road signs, guide boards, curved mirrors, soundproof walls; other greenhouses, large tanks, box tanks, bathroom parts, clock panels , Bathtub, sanitary, desk mat, game parts, toys, decorative film and protective film on the face such as mask for face protection during welding, wallpaper; marking film; LCD protective film, light guide film, Fresnel lens, lenticular lens, It is suitably used for optical parts such as front films and diffusion films of various displays.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “part” represents “part by mass” unless otherwise specified, and “%” represents “% by mass” unless otherwise specified.

Characteristic evaluation was performed according to the following method.
(1) Weight average molecular weight Using tetrahydrofuran as a solvent, Shodex (trademark) GPC SYSTEM11 manufactured by Showa Denko KK was connected to Shodex (trademark) KF-806L as a column for gel permeation chromatography, and Shodex (trademark) as a detector. It measured using the differential refractive index detector RI-101. The sample solution was prepared by accurately weighing 3 mg of resin, dissolving it in 3 ml of tetrahydrofuran, and filtering the solution through a 0.45 μm membrane filter. The flow rate during measurement was 1.0 ml / min. The weight average molecular weight (Mw) was calculated as the molecular weight in terms of polymethyl methacrylate based on a calibration curve prepared with standard polymethyl methacrylate manufactured by Polymer Laboratories.

(2) Glass transition temperature (Tg)
The main dispersion peak temperature (Tg) of loss tangent (tan δ) is injection molded from an acrylic resin composition used to produce a molded body using EXSTAR6000 DMS manufactured by SII Nano Technology. A rectangular parallelepiped test piece having a length of 60 mm, a width of 10 mm, and a thickness of 4 mm obtained by cutting the test piece obtained in this manner in a bending mode (both-end supported beam measurement) has a sinusoidal vibration of 10 Hz, a heating rate of 3 ° C. / min. It was measured by.

(3) Measurement of surface roughness of molded body and laminate The shape of the surface was measured by the DFM mode using an atomic force microscope (SPI 4000 probe station E-sweep environment control unit manufactured by SII Nanotechnology). SI-DF20 (back Al) manufactured by SII Nano Technology was used as the probe. (Before sample measurement, a reference sample with a pitch of 10 μm and a step of 100 nm is measured, and the measurement error of the X-axis and Y-axis of the apparatus is 5% or less for 10 μm, and the error of the Z-axis is 5% or less for 100 nm I confirmed it.)

The observation area of the sample was 2 μm × 2 μm, and the measurement frequency was 1.0 Hz. The number of scan lines was 512 on the X axis and 512 on the Y axis. The measurement was performed in an atmospheric environment at 25 ° C. ± 2 ° C. and humidity 30 ± 5%. The obtained measurement data was analyzed by data processing software attached to the apparatus, and the average surface roughness Ra was obtained. That is, after selecting the [Third-order tilt correction] command in the [Tool] menu of the measurement software of the apparatus and correcting the tilt of the formed body or the laminate or the overall tilt of the large waviness, the [Surface roughness] of the [Analysis] menu is selected. The [Analysis] command was selected to obtain the average surface roughness Ra. The average surface roughness Ra is defined as follows.
* Average surface roughness Ra: A value obtained by averaging the absolute values of deviations from the reference surface to the specified surface.

ここでＦ（Ｘ，Ｙ）は（Ｘ，Ｙ）座標での高さの値を表す。Ｚ₀は以下で定義されるＺデータの平均値を表す。

Here, F (X, Y) represents a height value in the (X, Y) coordinates. Z ₀ represents the average value of Z data defined below.

また、Ｓ₀は、測定領域の面積を表す。

S ₀ represents the area of the measurement region.

This average surface roughness Ra was measured at 10 different regions on both surfaces (for convenience, the A surface and the B surface) of the molded body (film or plate), and the average value of the 10 average surface roughness Ra was determined. The roughness of the surface of the compact was taken. Moreover, it measured in 10 different area | regions in the metal vapor deposition surface of a laminated body, and made the average value of 10 average surface roughness Ra the roughness of the laminated body surface.
The cubic inclination correction was performed by fitting the measured sample surface with a cubic surface by least square approximation to eliminate the influence of the inclination and waviness of the sample.

(4) Handleability (cutability of laminate)
Dumbbell Super Circular Cutter (model SDRK-1000-D) is attached to Dumbbell SDL-200 lever type sample cutter, and metal is placed on Dumbbell Mount (size: 160mm x 200mm x 3mm) When a laminate having a metal oxide layer on one side is placed and a round test piece having a diameter of 25.12 mm is punched 10 times from the laminate, cracks other than the shape of the round test piece are introduced 10 times. The case where there was no crack was evaluated as ◯, the case where cracks occurred once or more in addition to the shape of the circular test piece, and the case where cracks entered all 10 times other than the shape of the circular test piece were evaluated as x.

(5) Specular Gloss of the Laminate Formed with Metal and / or Metal Oxide Layer According to JIS Z8741 Method 3, the 60-degree specular gloss was measured.

(6) Presence or absence of a portion of the laminate in which the metal and / or metal oxide layer is not deposited with aluminum (defects) The side of the laminate on which the aluminum is deposited is visually observed, and the aluminum is deposited. The case where there was no portion (defect) was evaluated as x, and the case where there was no portion (defect) where aluminum was not deposited was evaluated as ◯.

(7) Surface hardness of laminated body The pencil hardness of the laminated body surface (B surface) on the opposite side of the surface on which the metal and / or metal oxide layer was formed was measured according to JIS K5400.

[Methacrylic resin]
A methacrylic resin composed of methyl methacrylate units and methyl acrylate units in the ratios shown in Table 1 was prepared by bulk polymerization. Table 1 shows the weight average molecular weight (Mw) and glass transition temperature (Tg _A ) of the prepared methacrylic resin.

[Polyvinyl acetal resin]
An aldehyde compound and an acid catalyst (hydrochloric acid) were added to an aqueous solution in which the polyvinyl alcohol resin was dissolved, and the mixture was stirred to acetalize to precipitate the resin. Washed to pH = 6 according to known methods, then suspended in alkaline aqueous medium and worked up with stirring, washed again to pH = 7, volatiles to 1.0% The polyvinyl acetal resin shown in Table 2 was obtained by drying until it became.

The degree of acetalization of the polyvinyl acetal resin was determined by the following procedure.
First, in accordance with the method described in JIS K6728 (1977), the mass ratio (l ₀ ) of the vinyl alcohol unit and the mass ratio (m ₀ ) of the vinyl acetate unit were determined by the methods described below. The mass ratio (k ₀ ) was determined by k ₀ = 1−l ₀ −m ₀ .
_{Then, l = (l 0 /44.1)/(l 0} /44.1+m 0 /86.1+2k 0 / Mw (acetal)) and _{m = (m 0 /86.1)/(l 0/} 44 .1 + m ₀ /86.1+2k ₀ / Mw (acetal)) by calculation, and the ratio of vinyl acetal units (k = k ₍₁₎ + k ₍₂₎ +... + K _(n) ), and finally the degree of acetalization (mol%) = {k ₍₁₎ + k ₍₂₎ +... + K _(n) } × 2 / {{k ₍₁₎ + k _{(2 )} +... + K _(n) } × 2 + l + m} × 100.
Here, Mw (acetal) is the molecular weight per acetalization unit. For example, in the case of polyvinyl butyral, Mw (acetal) = Mw (butyral) = 142.2.
In the case of coacetalization with butyraldehyde and other aldehydes, ¹ H-NMR or ¹³ C-NMR can be measured, and the degree of acetalization (mol%) can be calculated.

[How to find l ₀ and m ₀ ]
About 0.4 g of polyvinyl acetal resin is accurately weighed into a conical Erlenmeyer flask, dissolved by adding 10 ml of a mixed solution of pyridine / acetic anhydride (volume ratio 92/8) with a pipette, and attached with a cooler at a temperature of 50 ° C. On a water bath for 120 minutes. After cooling, 20 ml of dichloroethane was added and shaken well. Further, 50 ml of water was added, stoppered and shaken vigorously, and allowed to stand for 30 minutes. The acetic acid produced is titrated with N / 2 sodium hydroxide solution with phenolphthalein as an indicator until it turns pale red, and the titration is defined as a (ml). Separately, a blank test was performed, and the titration amount of the N / 2 sodium hydroxide solution required for this was defined as b (ml), and obtained by the following formula.
l ₀ = 2.2 × (ba) × F _l / (s _l × P _l )
In the formula, s _{1 is} the mass of the polyvinyl acetal resin, P ₁ is the pure content (%), and F ₁ is the titer of the N / 2 sodium hydroxide solution.
Also, weigh accurately about 0.4 g of polyvinyl acetal resin in a conical flask with a stirrup, add 25 ml of ethanol and dissolve at 85 ° C., add 5 ml of N / 10 sodium hydroxide solution while shaking well with a pipette, and cool. The vessel was attached and refluxed in a water bath at a temperature of 85 ° C. for 60 minutes. After cooling, 5 ml of N / 10 hydrochloric acid was added with a pipette, shaken well, and allowed to stand for 30 minutes. Excess hydrochloric acid was titrated with a N / 10 sodium hydroxide solution using phenolphthalein as an indicator until a slight red color was obtained, and the titer was c (ml). Separately, a blank test was carried out, and the titration amount of the N / 10 sodium hydroxide solution required for this was determined as d (ml), and obtained by the following formula.
m ₀ = 0.86 × (cd) × F _m / (s _m × P _m )
In the formula, s _{m is} the mass of the polyvinyl acetal resin, P _m is the pure content (%), and F _m is the titer of the N / 10 sodium hydroxide solution.

Example 1
A cylinder temperature of 220 ° C. using 75 parts of methacrylic resin (A-1) and 25 parts of polyvinyl acetal resin (B-1) using a twin screw kneading extruder TEX-44α (L / D = 40) manufactured by Nippon Steel. The mixture was kneaded at a screw rotation speed of 200 rpm to obtain thermoplastic resin composition pellets. The resin temperature measured just before the die of the extruder at that time was 233 ° C. Maximum shear rate of the extruder is 300 sec ^-1, shear rates in the clearance large portion of the barrel and the screw elements were 45 sec ^-1. Screw, the rotational speed of the used was a structure in which the shear shear and 45 sec ^-1 of 300 sec ^-1 is applied twice alternately.
The pellets of the obtained thermoplastic resin composition were injection-molded at a cylinder temperature of 240 ° C. using J50E2 manufactured by Nippon Steel Works to obtain a rectangular parallelepiped test piece having a length of 80 mm × width of 10 mm × thickness of 4 mm. Furthermore, by cutting the rectangular parallelepiped test piece, to obtain a rectangular test piece of length 60 mm × width 10 mm × thickness 4 mm, it was measured Tg _AP.
The obtained pellets were extruded from a T-die having a width of 500 mm using GT-40 manufactured by Plastics Engineering Laboratory, and the pressure was adjusted to 50 N / mm with two metal mirror rolls adjusted to 90 ° C. immediately below the T-die. The film having a thickness of 100 μm was obtained. Table 3 shows the roughness of the surface of this film (for convenience, the surface with low roughness is referred to as surface A and the surface with high roughness as surface B. The same applies hereinafter).
The A side of this film was subjected to corona discharge treatment, and then aluminum was deposited on the A side by a vacuum deposition method. The thickness of the aluminum layer was 30 nm. The roughness of the vapor-deposited surface of the laminate thus obtained, handleability (cutability of the laminate), 60 ° specular gloss, presence of defects, and surface hardness were evaluated. Table 3 shows the results.

Example 2
Example 1 Example 1 except that the film is not sandwiched between two metal mirror rolls directly under the T die, and the film is brought into contact with only one mirror metal roll whose temperature is adjusted to 90 ° C., and one side is opened to the air. In the same manner as in Example 1, a film having a thickness of 100 μm was obtained. Table 3 shows the roughness of the surface of the film. Further, the A side of the film was subjected to corona discharge treatment, and then aluminum was deposited on the A side by a vacuum deposition method. The thickness of the aluminum layer was 30 nm. The roughness of the vapor-deposited surface of the laminate thus obtained, handleability (cutability of the laminate), 60 ° specular gloss, presence of defects, and surface hardness were evaluated. Table 3 shows the results.

Example 3
A laminate was obtained in the same manner as in Example 1 except that the thickness of the aluminum layer in Example 1 was changed to 10 nm. The roughness of the deposited surface of this laminate, the handleability (cutability of the laminate), 60 ° specular gloss, presence of defects, and surface hardness were evaluated. Table 3 shows the results.

Example 4
A methacrylic resin (A-2) and a polyvinyl acetal resin (B-1) are kneaded at a blending amount shown in Table 3 using a twin screw kneading extruder TEX-44α (L / D = 40) manufactured by Japan Steel Works. To obtain pellets.
The obtained pellets were extruded from a T-die having a width of 500 mm using GT-40 manufactured by Plastics Engineering Laboratory, and the pressure was adjusted to 50 N / mm with two metal mirror rolls adjusted to 90 ° C. immediately below the T-die. The plate-shaped molded object of thickness 2mm was obtained. Table 3 shows the roughness of the surface of this molded body (for the sake of convenience, the surface with low roughness is referred to as surface A and the surface with high roughness as surface B. The same applies hereinafter).
Further, corona discharge treatment was applied to the A surface of the plate-shaped molded body, and then aluminum was deposited on the A surface by a vacuum deposition method. The thickness of the aluminum layer was 30 nm. The thus obtained laminate was evaluated for roughness, handleability (laminate cutability), 60 ° specular gloss, presence of defects, and surface hardness. Table 3 shows the results.

Example 5
A laminate was obtained in the same manner as in Example 1 except that pellets obtained from the methacrylic resin (A-1) and the polyvinyl acetal resin (B-2) having the formulation shown in Table 3 were used. The roughness, handleability (lamination of the laminate), 60-degree specular gloss, presence of defects, and surface hardness of this laminate were evaluated. Table 3 shows the results.

Example 6
A laminate was obtained in the same manner as in Example 1 except that pellets obtained from the methacrylic resin (A-1) and the polyvinyl acetal resin (B-3) having the formulation shown in Table 3 were used. The roughness, handleability (lamination of the laminate), 60-degree specular gloss, presence of defects, and surface hardness of this laminate were evaluated. Table 3 shows the results.

Examples 7 and 8
A laminate was obtained in the same manner as in Example 1 except that pellets obtained from the methacrylic resin (A-1) and the polyvinyl acetal resin (B-1) having the formulation shown in Table 3 were used. The roughness, handleability (lamination of the laminate), 60-degree specular gloss, presence of defects, and surface hardness of this laminate were evaluated. Table 3 shows the results.

Comparative Example 1
Two metal mirror surfaces that were extruded from a 500 mm wide T-die using GT-40 manufactured by Plastics Engineering Laboratory using only methacrylic resin (A-1), and the temperature was adjusted to 90 ° C. immediately below the T-die. A film having a thickness of 100 μm was obtained by sandwiching with a roll at a pressing pressure of 50 N / mm. Table 3 shows the roughness of the surface of the film. Further, the A side of the film was subjected to corona discharge treatment, and then aluminum was deposited on the A side by a vacuum deposition method. The thickness of the aluminum layer was 30 nm. The roughness of the vapor-deposited surface of the laminate thus obtained, handleability (cutability of the laminate), 60 ° specular gloss, presence of defects, and surface hardness were evaluated. Table 3 shows the results.

Comparative Example 2
A methacrylic resin (A-1) and a polyvinyl acetal resin (B-1) are kneaded at a blending amount shown in Table 3 using a Nippon Steel Works twin screw kneading extruder TEX-44α (L / D = 40). To obtain pellets. The obtained pellets were extruded from a T-die having a width of 500 mm using GT-40 manufactured by Plastics Engineering Laboratory, and the pressure was adjusted to 50 N / mm with two metal mirror rolls adjusted to 90 ° C. immediately below the T-die. The film having a thickness of 100 μm was obtained. Table 3 shows the roughness of the surface of the film. Further, the A side of the film was subjected to corona discharge treatment, and then aluminum was deposited on the A side by a vacuum deposition method. The thickness of the aluminum layer was 30 nm. The roughness of the vapor-deposited surface of the laminate thus obtained, handleability (cutability of the laminate), 60-degree specular gloss, presence of defects, and surface hardness were evaluated. Table 3 shows the results.

  As shown in Table 3, a laminate (Comparative Example 1) in which a metal film is provided on a molded body obtained using only the methacrylic resin (A) is inferior in handleability. A laminate in which a metal film is provided on a molded body obtained using a material in which the mass ratio of the methacrylic resin (A) and the polyvinyl acetal resin (B) is out of the range of 99/1 to 51/49 (comparative example) 2) is inferior in specular gloss or surface hardness. On the other hand, the laminates (Examples) produced according to the present invention are excellent in handleability and have high specular gloss and surface hardness.

Claims (11)

A polyvinyl acetal resin having a degree of acetalization of 55 to 83 mol% obtained by (co) acetalizing a methacrylic resin [A] having a weight average molecular weight of 40000 or more and a polyvinyl alcohol resin having a number average degree of polymerization of 200 to 4000 [co]. B] in a mass ratio ([A] / [B]) 99/1 to 51/49, and the glass transition temperature Tg _{A of the} methacrylic resin (A) alone and the polyvinyl acetal resin (B ) On at least one surface of the acrylic resin molded article having a glass transition temperature Tg _AP due to the methacrylic resin (A) between the glass transition temperature Tg _B alone and
An acrylic resin laminate comprising a layer made of a metal and / or a metal oxide.   The acrylic resin laminate according to claim 1, wherein the acrylic resin molded body is a film, a sheet, or a plate.   3. The acrylic resin laminate according to claim 1, wherein the acrylic resin molded body has a roughness of 1.5 nm or less on a surface provided with a layer made of a metal and / or a metal oxide.   The acrylic resin laminate according to claim 2, wherein the roughness of both surfaces of the acrylic resin molded body is 1.5 nm or less.   The acrylic resin laminate according to any one of claims 1 to 4, wherein the acrylic resin molded body has a pencil hardness of H or higher.   The acrylic resin laminate according to claim 1, wherein the acrylic resin molded body has a thickness of 500 μm or less.   The acrylic resin laminate according to any one of claims 1 to 6, wherein printing is performed on at least one surface of the acrylic resin molded body.   The acrylic resin laminate according to any one of claims 1 to 7, wherein a layer made of another thermoplastic resin is further provided on one surface of the acrylic resin molded body.   A polyvinyl acetal resin having a degree of acetalization of 55 to 83 mol% obtained by (co) acetalizing a methacrylic resin (A) having a weight average molecular weight of 40000 or more and a polyvinyl alcohol resin having a number average degree of polymerization of 200 to 4000 (co). B) is melt-kneaded, extruded from a T-die in a molten state, and both surfaces thereof are brought into contact with a mirror roll surface or a mirror belt surface to form the acrylic resin molded body. The manufacturing method of the acrylic resin laminated body of crab.   The structure formed by adhere | attaching the film-form or sheet-form acrylic resin laminated body in any one of Claims 2-8 on the surface of a thermoplastic resin and / or a thermosetting resin. Inserting the film-like or sheet-like acrylic resin laminate according to any one of claims 2 to 8 between injection-moulded male and female molds,
The manufacturing method of a structure including the process of inject | pouring a thermoplastic resin into the metal mold | die from one side of this acrylic resin laminated body.