JP2011011543A - Alternative film for coating and laminated molding having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alternative film for coating showing a good balance of characteristics among stability of film-making, toughness, surface glossiness, surface hardness (pencil hardness), transparency and thermal resistance, and to provide a laminated molding using the same.SOLUTION: The alternative film for coating includes: 100 pts.mass of a heat-resistant acrylic resin (a) including ≥40 and ≤90 mass% of a methacrylate and/or acrylate unit, ≥5 and ≤40 mass% of an aromatic vinyl compound unit, and ≥5 and ≤30 mass% of a compound unit represented by the formula (1) wherein X is O or N-R, O is an oxygen atom, N is a nitrogen atom, and R is either one selected from a group including hydrogen atoms, an alkyl group, an aryl group and a cycloalkyl group; and ≥0.1 and ≤100 pts.mass of a multilayered rubbery polymer particle (b) having a refractive index by 0.015 or below smaller than that of the heat-resistant acrylic resin (a) and an average particle diameter of ≥0.04 and ≤0.13 μm.

Description

  The present invention relates to a paint substitute film and a laminated molded article including the paint substitute film.

The method of decorating the surface of a plastic product is roughly classified into a direct printing method and a transfer method.
The direct printing method is a method of directly printing on a molded product, and examples thereof include a pad printing method, a curved silk printing method, and an electrostatic printing method.
These direct printing methods are unsuitable when the molded product to be printed has a complicated shape, and it is difficult to impart a high degree of design.
On the other hand, the transfer method includes a thermal transfer method and a water transfer method, but has a problem of relatively high cost.

As a method other than the above, there is an in-mold molding method as a method for imparting design properties to a molded product at low cost.
In this method, the printed polyester resin, polycarbonate resin, acrylic resin sheet or film is formed in a three-dimensional shape by vacuum forming or the like in advance, or in a two-dimensional shape without molding. In this method, the resin used as a base material is injection molded by being inserted into an injection mold.
In this in-mold molding method, there are a case where the resin sheet or film and the base resin are integrated, and a case where only printing is transferred.
In this manner, once the sheet or film is decorated, the decoration sheet or film is bonded to the base material, thereby making it possible to substitute for painting.
By using the above-mentioned coating substitute film on the surface of a resin molded product, the design can be given depth and luxury to the molded product, and the simultaneous molding process can be used to reduce the painting process. It is possible to contribute to the reduction of environmentally hazardous substances.

In recent years, acrylic resin films suitable for laminating and in-mold molding have been disclosed as coating substitute films for luxury furniture materials and luxury automobile interior materials (see, for example, Patent Documents 1 and 2).
In addition, an acrylic resin film for paint replacement that has both plasticizer whitening resistance and moldability without sacrificing surface hardness and heat resistance is disclosed (for example, see Patent Document 3).
Furthermore, an acrylic resin film that is excellent in weather resistance, scratch resistance, chemical resistance, moldability, and visibility of a wood material and that exhibits high designability is disclosed (for example, see Patent Document 4).

JP-A-8-323934 Japanese Patent Laid-Open No. 11-147237 JP 2002-80678 A JP 2004-2739 A

By the way, in recent years, in order to cope with diversified use environments and advanced processing treatments, high heat resistance is required in addition to characteristics such as formability, surface hardness, and toughness. It is becoming. Specifically, this is a case where high-precision multicolor printing suitability, cutting, or thermoforming processing is required.
However, in the above-described prior art, sufficient characteristics have not yet been obtained, particularly with respect to heat resistance, among the characteristics of the film for paint replacement that requires added value in recent years.
Therefore, in the present invention, in view of the above-described problems of the prior art, a coating substitute film having a good balance of properties of film forming formability, toughness, surface glossiness, surface hardness (pencil hardness), transparency and heat resistance, and this The object is to obtain a laminated molded product using

As a result of intensive investigations on the above problems, the present inventors have found that the heat-resistant acrylic resin (a) having a specific composition ratio has a rubbery-containing copolymer having a multilayer structure in which the refractive index and the average particle diameter are controlled. It has been found that the problems of the prior art can be solved by blending the polymer particles (b) at a specific ratio, and the present invention has been completed.
Usually, improving the heat resistance of acrylic resin results in poor moldability, film-forming property and mechanical strength due to decrease in fluidity. Furthermore, fluidity, heat resistance and surface gloss are further reduced due to the inclusion of rubber. However, according to the present invention, the film forming moldability, toughness, surface glossiness, surface hardness (pencil hardness), transparency and heat resistance are well balanced. Coating substitute film made of a simple resin composition and a laminated molded body using the same.
The present invention is as follows.

[1]
Methacrylic acid ester and / or acrylic acid ester unit 40 mass% or more and 90 mass% or less, aromatic vinyl compound unit 5 mass% or more and 40 mass% or less, and compound unit 5 mass% represented by the following general formula (1) Heat-resistant acrylic resin (a) containing 30% by mass or less and 100 parts by mass,

(In the general formula (1), X represents O or N—R, O is an oxygen atom, N is a nitrogen atom, R is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a cycloalkyl group. Indicates either.)

Rubber-containing copolymer particles (b) having a multilayer structure having a refractive index difference with respect to the heat-resistant acrylic resin (a) of 0.015 or less and an average particle size of 0.04 μm or more and 0.13 μm or less: 0.1 parts by mass or more and 100 parts by mass or less,
A coating substitute film containing

[2]
The coating substitute according to [1], wherein the rubber-containing copolymer particles (b) are particles having a multilayer structure of three layers or more in which a hard layer, a soft layer, and a hard layer are formed from the inside. Film.

[3]
The coating substitute according to [1] or [2], wherein the film thickness is 200 μm or less, the haze value in a 23 ° C. environment is 2.0% or less, and the 60 ° surface glossiness is 120% or more. the film.

[4]
The coating substitute film according to any one of [1] to [3], wherein a haze value in an environment at 70 ° C. is 3.0% or less.

[5]
The coating substitute film according to any one of [1] to [4], wherein Tg (glass transition temperature) is 120 ° C. or higher.

[6]
The coating substitute film according to any one of [1] to [5], wherein a printed image is formed on one side.

[7]
A laminated molded product obtained by laminating the coating substitute film according to any one of [1] to [6] and a base material.

[8]
[7] In the above [7], the molding substitute film according to any one of [1] to [6] is subjected to a molding treatment, and then a resin is injection-molded on the coating substitute film to laminate a base material. The laminated molded article described.

  According to the present invention, it is possible to obtain a coating substitute film having a good balance of properties of film forming moldability, toughness, surface glossiness, surface hardness (pencil hardness), transparency and heat resistance, and a laminate molded body using the same. .

Hereinafter, although the form for implementing this invention (henceforth "this embodiment") is demonstrated, this invention is not limited to the form shown below.
In addition, in the following, the monomer component before superposition | polymerization is called "... monomer"("monomer" is abbreviate | omitted and may describe only a compound name.), And the structure which comprises a copolymer The unit is called “unit”.

[Painting substitute film]
The coating substitute film of the present embodiment has a methacrylic acid ester and / or acrylic ester unit unit of 40% by mass to 90% by mass, an aromatic vinyl compound unit of 5% by mass to 40% by mass, and the following general formula (1 Heat-resistant acrylic resin (a): 5 parts by mass or more and 30% by mass or less of a compound unit represented by:

(In the general formula (1), X represents O or N—R, O is an oxygen atom, N is a nitrogen atom, R is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a cycloalkyl group. Indicates either.)

Rubber-containing copolymer particles (b) having a multilayer structure having a refractive index difference with respect to the heat-resistant acrylic resin (a) of 0.015 or less and an average particle size of 0.04 μm or more and 0.13 μm or less: 0.1 parts by mass or more and 100 parts by mass or less,
Containing.

(Heat-resistant acrylic resin (a))
The heat-resistant acrylic resin (a) has a methacrylic acid ester and / or an acrylate unit as the first monomer component of 40 to 90% by mass, and an aromatic vinyl compound unit as the second monomer component. 5 mass% or more and 40 mass% or less, and 5 to 30 mass% of compound units represented by the said General formula (1) are contained as a 3rd monomer component.

<First monomer component: methacrylic acid ester and / or acrylic acid ester>
Examples of the methacrylic acid ester and / or acrylic acid ester that are the first monomer component of the heat-resistant acrylic resin (a) include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid. Methacrylic acid esters such as n-hexyl acid, cyclohexyl methacrylate, and t-butylcyclohexyl methacrylate; and acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, and 2-ethylhexyl acrylate . In particular, methyl methacrylate is preferred from the viewpoint of transparency and ease of polymerization.

<Second monomer component: aromatic vinyl compound>
Examples of the aromatic vinyl compound that is the second monomer component of the heat-resistant acrylic resin (a) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, Examples thereof include nuclear alkyl-substituted styrenes such as ethylstyrene and p-tert-butylstyrene; α-alkyl-substituted styrenes such as α-methylstyrene and α-methyl-p-methylstyrene. In particular, styrene is preferred from the viewpoints of heat decomposability and ease of polymerization.

<Third monomer component: Compound unit represented by formula (1)>
Among the compound units represented by the general formula (1) which is the third monomer component of the heat-resistant acrylic resin (a), those in which X is O include, for example, maleic anhydride, itaconic acid, ethyl Examples thereof include unsaturated dicarboxylic acid anhydride monomer units which are anhydrides such as maleic acid, methyl itaconic acid and chloromaleic acid. Among these, a maleic anhydride monomer unit is preferable from the viewpoint of heat decomposition resistance and heat resistance improvement.
Examples of X being N—R include maleimide monomer units such as N-phenylmaleimide and N-cyclohexylmaleimide.

  From the viewpoint of heat resistance and photoelastic coefficient, the copolymerization ratio of the monomer units constituting the heat-resistant acrylic resin (a) is 40 for the first monomer component: methacrylate ester and / or acrylate ester unit. % By mass to 90% by mass, second monomer component: aromatic vinyl compound unit of 5% by mass to 40% by mass, third monomer component: compound represented by the above general formula (1) A unit is 5 mass% or more and 30 mass% or less.

First monomer component: When the copolymerization ratio of methacrylic acid ester and / or acrylic acid ester unit is 40% by mass or more, optical characteristics and polymerization stability tend to be good, and 90% by mass or less. When it exists, it exists in the tendency for heat resistance to be maintained.
Further, when the copolymerization ratio of the second monomer component: aromatic vinyl compound unit is 5% by mass or more, the optical characteristics tend to be good, and when it is 40% by mass or less, the weather resistance is maintained. Tend to be.
Furthermore, the third monomer component: When the compound unit represented by the general formula (1) is 5% by mass or more, the heat resistance tends to be good, and when it is 30% by mass or less, coloring is performed. And polymerization stability tend to be maintained.

Preferably, the first monomer component: methacrylic acid ester and / or acrylic acid ester unit is 42% by mass or more and 83% by mass or less, and the second monomer component: aromatic vinyl compound unit is 12% by mass or more and 40% by mass or more. % By mass or less, third monomer component: the compound unit represented by the general formula (1) is 5% by mass or more and 18% by mass or less.
More preferably, the first monomer component: methacrylic acid ester and / or acrylic acid ester unit is 45% by mass or more and 78% by mass or less, and the second monomer component: aromatic vinyl compound unit is 16% by mass or more. 40 mass% or less, 3rd monomer component: The compound unit represented by the said General formula (1) is 6 mass% or more and 15 mass% or less.

The third monomer component: the copolymerization ratio of the second monomer component: aromatic vinyl compound unit to the copolymerization ratio of the compound unit represented by the general formula (1) is 1 to 3 times. The following is preferable.
When the ratio is in the above range, the effect of adding the aromatic vinyl compound can be easily obtained, and the yield of the polymer can be maintained in a certain range. Moreover, it is easy to dissolve in the monomer compounding phase, and the strength of the resin tends to be easily maintained.

The heat-resistant acrylic resin (a) includes a heat-resistant acrylic resin obtained by copolymerizing other monomers that can be copolymerized as necessary in addition to the above-described essential constituent monomer components. .
Examples of other copolymerizable monomers used here include unsaturated carboxylic acid monomers such as methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid and cinnamic acid; acrylonitrile, methacrylonitrile Unsaturated nitrile monomers such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3- Examples thereof include conjugated diene monomers such as hexadiene. These may be used alone or in combination of two or more.

<Method for producing heat-resistant acrylic resin (a)>
The heat-resistant acrylic resin (a) can be produced by bulk polymerization using a radical initiator, but can also be produced by solution polymerization or emulsion polymerization.
Aqueous suspension polymerization is not recommended when maleic anhydride is used as the monomer component, because its water solubility is high, and it tends to be difficult to maintain a stable suspension system throughout.
As the radical initiator, those generally used can be used, and in particular, peroxide initiators lauroyl peroxide, decanoyl peroxide, and t-butylperoxy 2-ethylhexanoate are used. Then, coloring of the heat-resistant acrylic resin (a) tends to be suppressed. Therefore, it is preferable to apply a diacyl peroxide such as lauroyl peroxide as a radical initiator when polymerizing the heat-resistant acrylic resin (a).
As a preferable polymerization method of the heat-resistant acrylic resin (a), for example, a method described in JP-B-63-1964 can be mentioned.

<Physical properties of heat-resistant acrylic resin (a)>
The melt index (ASTM D1238: I condition) of the heat-resistant acrylic resin (a) is preferably 10 g / 10 min or less, more preferably 6 g / 10 min or less, from the viewpoint of the strength of the coating substitute film of this embodiment. More preferably, it is 3 g / 10 minutes or less.

  The Tg (glass transition temperature) of the heat-resistant acrylic resin (a) is preferably 120 ° C. or higher, more preferably 125 ° C. or higher, and further preferably 130 ° C. or higher. When Tg is 120 ° C. or higher, thermal deformation under practical temperature conditions can be reduced in the coating substitute film of the present embodiment.

  The heat-resistant acrylic resin (a) may be a block polymer or a random polymer, but is preferably a statistically random polymer from the viewpoint of heat resistance, rigidity, and recyclability.

The molecular weight distribution range of the heat-resistant acrylic resin (a) is preferably such that the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 1.6 to 4.0. More preferably, it is 1.7-3.7, More preferably, it is the range of 1.8-3.5.
When Mw / Mn is 1.6 or more, the balance between the film processability and mechanical properties of the resin composition tends to be good.
Moreover, when Mw / Mn is 4.0 or less, the melt fluidity is improved and the processability tends to be good.
In addition, a weight average molecular weight (Mw), a number average molecular weight (Mn), and these ratio (Mw / Mn) can be calculated | required by polystyrene conversion using a gel permeation chromatography (GPC).

The weight average molecular weight (Mw) measured by GPC of the heat-resistant acrylic resin (a) is preferably 80,000 to 500,000, more preferably 90 to 300,000, and still more preferably 100 to 200,000.
When the weight average molecular weight (Mw) of the heat-resistant acrylic resin (a) is 500,000 or less, sufficient fluidity can be obtained at the time of extrusion stretching, so that melt extrusion and stretched film formation can be performed without major trouble. It is in.
Moreover, when the weight average molecular weight (Mw) of the heat-resistant acrylic resin (a) is 80,000 or more, good stretching stability and a sufficient degree of orientation tend to be imparted to the film.

(Rubber-containing copolymer particles (b))
The coating substitute film of this embodiment has a multilayer structure in which the difference in refractive index from the heat-resistant acrylic resin (a) described above is 0.015 or less and the average particle size is 0.04 μm or more and 0.13 μm or less. Including rubber-containing copolymer particles (b).

<Structure of (b)>
The rubber-containing copolymer particles (b) are not particularly limited as long as they satisfy the above characteristics, and rubber particles such as general butadiene-based ABS rubber, acrylic-based, polyolefin-based, silicone-based, and fluororubber. Can be used.
The rubber-containing copolymer particles (b) preferably have a multilayer structure having a three-layer structure or more, and more preferably acrylic rubber particles having a multilayer structure having a three-layer structure or more.
By using rubber particles having a multilayer structure of the three or more layers as the rubber-containing copolymer particles (b), deformation of the rubber-containing copolymer particles (b) due to heating is suppressed, and this embodiment The glass transition temperature (Tg) and transparency of the coating substitute film are practically good.

The rubber-containing copolymer particles (b) having a multilayer structure of three or more layers are rubber particles 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. It is more preferable that the particles have a three-layer structure formed in the order of hard layer-soft layer-hard layer from the inside.
By having the hard layer in the innermost layer and the outermost layer, deformation of the rubber-containing copolymer particles (b) tends to be suppressed, and the intermediate layer between the innermost layer and the outermost layer is soft. By containing a component, it exists in the tendency for the favorable toughness to be provided in the coating substitute film of this embodiment.

Specifically, when the rubber-containing copolymer particles (b) have a three-layer structure, the copolymer forming the innermost layer (bi) is 65 to 90% by mass of methyl methacrylate, It is preferable that this and other copolymerizable monomers 10-35 mass% which can be copolymerized are included.
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 (b) have a three-layer structure, the acrylate monomer in the copolymer that forms the innermost layer (bi) is not particularly limited. N-butyl acrylate and 2-hexyl acrylate are preferred.
As the aromatic vinyl compound monomer, the same monomers as those used for the heat-resistant acrylic resin (a) can be used, but preferably the refractive index of the innermost layer (bi) is set. From the viewpoint of adjusting and improving the transparency of the coating substitute film of the present embodiment, 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, One or more of 4-butanediol di (meth) acrylate, allyl (meth) acrylate, triallyl isocyanurate, diallyl maleate, divinylbenzene and the like can be used in combination. Among these, allyl (meth) acrylate is more preferable.

In the case where the rubber-containing copolymer particles (b) have a three-layer structure, the copolymer forming the intermediate layer (b-ii) contains 55 to 75% by mass of an acrylate ester and an acrylate ester. It is preferable to contain 25-45 mass% of other copolymerizable monomers which can superpose | polymerize.
Other copolymerizable monomers copolymerizable with the acrylate ester include 95% to 99.9% by weight of an aromatic vinyl compound monomer and 0.1% to 0.1% of a copolymerizable polyfunctional monomer. It is preferable that it contains 5 mass%.

When the rubber-containing copolymer particles (b) have a three-layer structure, the copolymer that forms the intermediate layer (b-ii) imparts excellent toughness in the coating substitute film of the present embodiment. From the viewpoint, a copolymer showing soft rubber elasticity is preferable.
Although it does not specifically limit as an acrylate ester which comprises the said intermediate | middle layer (b-ii), Preferably, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc. are mentioned. . These may be used alone or in combination of two or more. In particular, n-butyl acrylate and 2-hexyl acrylate are more preferable.
The aromatic vinyl compound monomer contained in the other copolymer monomer copolymerizable with the acrylate ester is the same as the monomer used in the heat-resistant acrylic resin (a) described above. From the viewpoint of improving the refractive index of the intermediate layer (b-ii) and improving the transparency of the coating substitute film of this embodiment, styrene or a derivative thereof is preferably used. It is done.
The copolymerizable polyfunctional monomer contained in the other copolymer monomer copolymerizable with the acrylate ester is a copolymerizable polyfunctional monomer used in the innermost layer (bi) described above. The thing similar to a monomer can be used. The content of the copolymerizable polyfunctional monomer is such that other copolymerizable monomers copolymerizable with the acrylate ester, that is, other copolymerizable monomers copolymerizable with the acrylate ester. When 100% by mass is 0.1% by mass or more and 5% by mass or less, the toughness of the coating substitute film of the present embodiment has a good crosslinking effect, and the crosslinking is moderate and the rubber elastic effect is increased. Tends to be improved.

  When the rubber-containing copolymer particles (b) have a three-layer structure, the copolymer forming the outermost layer (b-iii) is 70 to 100% by mass of methyl methacrylate and can be copolymerized therewith. It is preferable that it contains 0-30 mass% of other copolymerizable monomers.

  Although it does not specifically limit as another copolymerizable monomer which can be copolymerized with methyl methacrylate which forms the said outermost layer (b-iii), N-butyl acrylate and 2-hexyl acrylate are preferable. It is mentioned as a thing.

<Method for Producing Rubber-Containing Copolymer Particles (b)>
The method for producing the rubber-containing copolymer particles (b) is not particularly limited, and can be produced by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In particular, it is preferable to obtain by emulsion polymerization. In this case, in the presence of an emulsifier and an initiator, the monomer mixture of the innermost layer (bi) is first added to complete the polymerization, and then the monomer mixture of the intermediate layer (b-ii) is added. By completing the polymerization and then adding the monomer mixture of the outermost layer (b-iii) to complete the polymerization, the multilayer structure particles can be easily obtained as a latex. The rubber-containing copolymer particles (b) can be recovered from the latex as a powder by a known method such as salting out, spray drying, freeze drying and the like.

<Physical properties of rubber-containing copolymer particles (b)>
The rubber-containing copolymer particles (b) have a refractive index difference of 0.015 or less, more preferably 0.012 or less, and still more preferably 0.01 or less, with the heat-resistant acrylic resin (a) described above. is there.
When the refractive index difference between the rubber-containing copolymer particles (b) and the heat-resistant acrylic resin (a) is 0.015 or less, a coating substitute film excellent in transparency can be obtained.

  Examples of the method for satisfying the refractive index difference between the rubber-containing copolymer particles (b) and the heat-resistant acrylic resin (a) include monomers of the heat-resistant acrylic resin (a). And / or a method of adjusting the composition ratio of the polymer and monomer in each layer constituting the rubber-containing copolymer particles (b).

As a method for measuring the refractive index difference between the rubber-containing copolymer particles (b) and the heat-resistant acrylic resin (a), first, in the rubber-containing copolymer particles (b), 1.59 and 1.49, respectively. Are mixed with the rubber-containing copolymer particles (b) while changing the ratio, and the point at which the white turbidity disappears is determined by the refractive index of the rubber-containing copolymer particles (b) (23 ° C., 550 nm).
And it calculates | requires by calculating the difference with the refractive index of the heat-resistant acrylic resin (a) press-molded separately measured with the laser refractometer.

The rubber-containing copolymer particles (b) have an average particle size of 0.04 μm or more and 0.13 μm or less, preferably 0.05 μm or more and 0.1 μm or less, more preferably 0.055 μm or more and 0.08 μm, Preferably they are 0.06 micrometer or more and 0.075 micrometer.
If the average particle size of the rubber-containing copolymer particles (b) is 0.04 μm or more, the toughness of the coating substitute film of this embodiment can be maintained, and if it is 0.13 μm or less, the coating of this embodiment The transparency of the substitute film can be kept at a practically good value.
In particular, when the coating substitute film of this embodiment has a thickness of 100 μm or less, the average particle diameter of the rubber-containing copolymer particles (b) is 0.1 μm or less in order to maintain transparency. The average particle size of the rubber-containing copolymer particles (b) is preferably 0.08 μm or less so that the haze value is 3.0% or less under high temperature conditions (70 ° C.).
The average particle diameter of the rubber-containing copolymer particles (b) is obtained by sampling the emulsion of the rubber-containing copolymer particles, diluting with water, and measuring the absorbance using a predetermined spectrophotometer. Thus, the sample whose particle diameter was measured from a transmission electron micrograph was obtained using a calibration curve prepared by measuring the absorbance in the same manner.

<Content of rubber-containing copolymer particles (b)>
The content of the rubber-containing copolymer particles (b) described above is the above-described heat-resistant acrylic resin (a) 100 from the viewpoints of trimming properties, folding strength, and transparency of the coating substitute film of this embodiment. It shall be 0.1 to 100 parts by mass, preferably 5 to 80 parts by mass, more preferably 10 to 65 parts by mass, and even more preferably 15 parts by mass with respect to parts by mass. The amount is 50 parts by mass or less.
When the content of the rubber-containing copolymer particles (b) is 100 parts by mass of the heat-resistant acrylic resin (a), the coating substitute film has a trimming property and bending strength of 0.1 parts by mass or more. In the trimming process, microcracks and cracks can be suppressed. When it is 100 parts by mass or less, the heat resistance and transparency of the coating substitute film can be maintained at practically good values.
In addition, a trimming process means the process of cutting off both ends in order to make the film width uniform when manufacturing a film for painting substitute. At this time, if the film is inferior in trimming property, microcracking or cracking phenomenon occurs during the cutting process, and the productivity of the film is remarkably lowered.

(Components other than (a) component and (b) component)
<Other polymers>
In the coating substitute film of the present embodiment, other polymers than the above-mentioned (a) heat-resistant acrylic resin and (b) rubber-containing copolymer particles are mixed within a range not impairing the effects of the present invention. can do.
Examples of such other polymers include polyolefin resins such as polystyrene, polyethylene, and polypropylene, polyamide resins, polyphenylene sulfide resins, polyether ether ketone resins, polyesters, polysulfones, polyphenylene oxides, polyimides, polyether imides, polyacetals, and the like. And thermosetting resins such as phenol resins, melamine resins, silicone resins, and epoxy resins.

<Additives>
Moreover, arbitrary additives can be mix | blended with the coating substitute film of this embodiment within the range which does not impair the effect of this invention according to various objectives.
The type of additive is not particularly limited as long as it is generally used for compounding resins, for example, inorganic fillers such as silicon dioxide, pigments such as iron oxide, stearic acid, behenic acid, zinc stearate, Lubricants such as calcium stearate, magnesium stearate, ethylene bisstearamide, mold release agents, paraffinic process oil, naphthenic process oil, aromatic process oil, paraffin, organic polysiloxane, mineral oil, etc. Agents, flame retardants, antistatic agents, organic fibers, glass fibers, carbon fibers, reinforcing agents such as metal whiskers, and coloring agents. These may be used alone or in combination of two or more.

<Heat stabilizer>
The coating substitute film of the present embodiment has a hindered phenolic antioxidant and / or phosphorus antioxidant as a thermal stabilizer within the range that does not impair the effects of the present invention in order to stabilize the film forming property. An antioxidant such as an agent can be blended. In particular, a hindered phenol antioxidant is preferable.
Examples of the hindered phenol antioxidant include pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), thiodiethylene-bis (3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis (3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide), diethyl ((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) phosphate, 3,3 ' , 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, ethyl Renbis (oxyethylene) bis (3- (5-t-butyl-4-hydroxy-m-tolyl) propionate), hexamethylene-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate), 1,3,5-tris (3,5-di-t-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-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 3,9-bis (2- (3- (3 -T-butyl-4-hydroxy-5-methylphenyl Propionyloxy) -1,1-dimethylethyl) -2,4,8,10-spiro (5,5) undecane.

  Commercially available phenolic antioxidants may be used as hindered phenolic antioxidants. Examples of such commercially available phenolic antioxidants include 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 (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: 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, manufactured by Ciba Specialty Chemicals), Sumitizer BHT (Sumilizer BHT, Sumitomo Chemical), Cyanox 1790 (Cyanox 1790, manufactured by Cytec), Sumilizer GA-80 (Sumizer GA-80, manufactured by Sumitomo Chemical), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo Chemical), Vitamin E (manufactured by Eisai), etc. Be mentioned Among these, Irganox 1010, Irganox 1076, Sumilizer GS, etc. are particularly preferable, and these may be used alone or in combination of two or more.

  Examples of phosphorus antioxidants 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′-diylbisphosphonite, 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′-diylbisphosphonite, di-t-butyl-m-cresyl-phosphonite, etc. And the like.

  A commercially available phosphorus antioxidant may be used as the phosphorus antioxidant. Examples of such commercially available phosphorus antioxidants include Irgafos 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: Bis (2,4-bis (1,1-dimethylethyl) ) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by Ciba Specialty Chemicals), ADK STAB 329K (ADK ST) B 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) GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE), Sumilyzer GP (Sumilizer GP, manufactured by Sumitomo Chemical), and the like. These may be used alone or in combination of two or more.

<Ultraviolet absorber>
Furthermore, an ultraviolet absorber can be added to the coating substitute film of this embodiment as long as the effects of the present invention are not impaired.
Examples of ultraviolet absorbers include benzotriazole compounds, benzotriazine compounds, benzoate compounds, benzophenone compounds, oxybenzophenone compounds, phenol compounds, oxazole compounds, malonic ester compounds, cyanoacrylate compounds, Examples include lactone compounds, salicylic acid ester compounds, benzoxazinone compounds, hindered amine compounds, and triazine compounds. These ultraviolet absorbers may be used alone or in combination of two or more.

In order to ensure excellent moldability in the coating substitute film of the present embodiment, the ultraviolet absorber preferably has a vapor pressure (P) at 20 ° C. of 1.0 × 10 ⁻⁴ Pa or less, more Preferably it is 1.0 * 10 <^-6> Pa or less, More preferably, it is 1.0 * 10 <^-8> Pa or less.
Here, being excellent in molding processability means, for example, that a low molecular compound adheres less to a roll at the time of forming a coating substitute film. For example, when a low molecular weight compound adheres to a roll, the low molecular weight compound adheres to the film surface via the roll and deteriorates the appearance and optical properties of the film, which is not preferable as an optical material. Here, the low molecular weight compound means, for example, a thermal decomposition product or a volatile matter derived from an ultraviolet absorber.

  Further, in order to ensure excellent molding processability in the coating substitute film of the present embodiment, the ultraviolet absorber preferably has a melting point (Tm) of 80 ° C. or higher, more preferably 130 ° C. or higher. More preferably, the temperature is 160 ° C. or higher.

  Further, in order to ensure excellent molding processability in the coating substitute film of the present embodiment, the ultraviolet absorber has a weight reduction rate when the temperature is increased from 23 ° C. to 260 ° C. at a rate of 20 ° C./min. It is preferably 50% or less, more preferably 15% or less, and further preferably 2% or less.

[Production method of paint substitute film]
About the manufacturing method of the film for coating substitutes of this embodiment, it does not restrict | limit in particular, Heat-resistant acrylic resin (a), rubber-containing copolymer particle (b), and the other mentioned above as needed It can manufacture by a well-known method by using the polymer of this, an additive, etc. as a raw material.
For example, by using a melt kneader such as a single screw extruder, twin screw extruder, Banbury mixer, Brabender, various kneaders, etc., a resin composition containing the components (a) and (b) described above is manufactured, It can be manufactured by extruding an original film or sheet using an extruder equipped with a T die, a circular die, or the like.
In the case of obtaining a coating substitute film by extrusion molding, a material obtained by previously melting and kneading the components (a) and (b) may be used, or molding may be performed through melt kneading at the time of extrusion molding.
Moreover, if it is a thin film molded product, it can shape | mold by well-known methods, such as blow molding, injection blow molding, inflation molding, foaming molding, and you may apply secondary process shaping | molding methods, such as pressure forming and vacuum forming.

In addition, the coating substitute film can be printed by an appropriate printing method as necessary in order to impart designability to a predetermined molded product.
In this case, it is preferable to perform a one-side printing process to obtain a film having a pattern or the like printed on one side.

The coating substitute film of this embodiment has a film thickness of preferably 200 μm or less, more preferably 10 μm to 150 μm, and still more preferably 20 μm to 100 μm.
In particular, by setting the film thickness to 50 μm or more and 150 μm or less, a sufficient depth can be obtained as an appearance when it is attached to a molded product, and a sufficient thickness can be ensured even if the film is stretched even when molded into a complicated shape. it can.

[Physical properties of paint substitute films]
(Haze value: Turbidity)
The coating substitute film of the present embodiment has a haze value (turbidity) in an environment of 23 ° C., which is one of the indices representing transparency, preferably 2.0% or less, more preferably 1.0% or less. is there. When the haze value in an environment of 23 ° C. is 2.0% or less, high transparency tends to be imparted to the coating substitute film.

  Furthermore, the coating substitute film of the present embodiment has a haze value in a 70 ° C. environment of preferably 3.0% or less, more preferably 2.0% or less. When the haze value in an environment of 70 ° C. is 3.0% or less, for example, when used outdoors, a decrease in transparency due to a temperature rise tends to be suppressed.

(Glass-transition temperature)
The coating substitute film of this embodiment has a Tg (glass transition temperature) of practically preferably 120 ° C. or higher, more preferably 125 ° C. or higher, and further preferably 130 ° C. or higher.
When the glass transition temperature is 120 ° C. or higher, thermal deformation of the film in a processing step, use environment, or the like is suppressed.
Furthermore, when the coating substitute film of this embodiment is used for a vehicle, the glass transition temperature is 110 ° C. or higher, for example, it can be used in the vicinity of the handle portion, but Tg is 120 ° C. or higher. For example, it can be used in the vicinity of a meter panel portion, so that the industrial utility value is increased.
Tg (glass transition temperature) can be measured by the same method as shown in Examples described later.

(Folding strength)
The folding substitute film in the present embodiment has a folding strength in the direction perpendicular to MD of preferably 1.0 or more, more preferably 1.5 or more, and further preferably 2.0 or more.
Here, the folding strength refers to a value obtained by logging the number of folding times determined according to JIS P 8115 (International Organization for Standardization: ISO 5626).
When the folding strength in the direction perpendicular to MD is 1.0 or more, when used as a coating substitute film, the film is hardly cracked and can be processed into a complicated molded surface.
In addition, MD shows the mechanical flow direction in film forming.

(Pencil hardness, surface gloss)
In order to form a sufficiently thick coating film on the molded product by painting, it is necessary to apply several dozen times, which is costly and extremely deteriorated in productivity. If the film for use is used, since the coating substitute film itself functions as a coating film, a thick coating film can be easily formed, which is industrially advantageous.
Such a coating substitute film preferably has, for example, a pencil hardness (measurement based on JIS K5400) of H or higher and a 60 ° surface glossiness of 120% or higher.
When the pencil hardness is H or more, scratches during handling are reduced, and the surface smoothness after the hard coat treatment tends to be good.
Further, when the 60 ° surface glossiness is 120% or more, the surface appearance becomes good, preferably 130% or more, more preferably 140% or more.

(Laminated molded product)
The laminated molded product of this embodiment has a configuration in which the above-described coating substitute film and a predetermined base material are laminated.
The resin constituting the substrate is preferably one that can be melt-bonded to the above-described coating substitute film.
For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or various resins containing these as main components can be used.
From the viewpoint of adhesiveness, an ABS resin, an AS resin, a polycarbonate resin, a vinyl chloride resin, or a resin containing these resins as a main component is preferable, and an ABS resin, a polycarbonate resin, or a resin containing these resins as a main component is more preferable.
In addition, even if it is resin which does not melt-melt, such as polyolefin resin, it can be used as a base material of the film for coating substitutes by interposing a predetermined contact bonding layer.

[Production method of laminated molded product]
The laminated molded product of this embodiment can be manufactured by laminating the above-described coating substitute film and a separately molded base material.
That is, the coating substitute film may be laminated by a conventionally known lamination method such as thermal lamination. It can bond together via the adhesive agent with respect to the base material of the material which is not heat-seal | fused.
In addition, the laminated molded product of the present embodiment may be manufactured by performing a molding process on the coating substitute film, then injection-molding a predetermined resin, and laminating the coating substitute film and the base material. it can.
This method is suitable for manufacturing a three-dimensional shape as the laminated molded body of the present embodiment.
Specifically, conventionally known molding methods such as an insert molding method and an in-mold molding method can be applied. In particular, the in-mold molding method is preferable from the viewpoint of productivity.
In the in-mold molding method, after heating the coating substitute film, vacuum molding is performed in a mold having a vacuum drawing function.
The heating temperature is preferably equal to or higher than the temperature at which the coating substitute film is softened.
Specifically, although it depends on the thermal properties of the coating substitute film and the shape of the target laminated molded product, it is usually set to 70 ° C. or higher and 170 ° C. or lower. As a result, the surface appearance becomes good, and a practically sufficient releasability can be secured.
As described above, when a three-dimensional shape is imparted to the film by vacuum forming, it is important to have followability to the mold corner. That is, the coating substitute film is advantageous for the molding method when it has a high degree of elongation at high temperatures.
After imparting a three-dimensional shape to the film by vacuum forming, the film and the base resin are melted and integrated by injection molding to obtain a laminated molded product having a coating substitute film layer on the surface layer.
The method described above is an excellent method from the viewpoints of workability and economy because it can form the coating substitute film and the injection molding of the substrate in one step.

The laminated molded product of the present embodiment can be given a desired design by using it as a substitute material for coating a predetermined molded body.
In order to impart design properties, printing is performed on the coating substitute film surface by an appropriate printing method as necessary.
By making the printing surface of the coating substitute film a laminated surface with the base material, the printing surface can be protected and a visually high-class feeling can be imparted.
In this case, the material of the base material can be utilized to give a matte feeling such as transparency, depth, and luxury, or to add a predetermined color tone.

[Applications for paint substitute films and laminated moldings]
The application of the above-described coating substitute film and laminated molded product is not particularly limited. For example, automobile interior parts such as console boxes and shift lever boxes, vehicle exterior parts such as motorcycle cowlings, home appliances, furniture, building materials, and mobile phones It can also be used for parts that have been painted in the past, such as telephones, and is very useful in these applications.

  Examples of the present invention and comparative examples will be specifically described below, but the present invention is not limited to the examples described below.

〔Measuring method〕
The physical property measurement method and evaluation method applied in the examples and comparative examples are shown below.
(1) Measurement of glass transition temperature (Tg) In DSC-7 type (manufactured by Perkin Elmer Co., Ltd.), in a temperature increase measurement from room temperature to 200 ° C., the raw film sample mass 8 at a temperature increase rate of 20 ° C./min. 0.0 to 10 mg of Tg was measured.

(2) Measurement of average particle diameter of rubber-containing copolymer particles (b) An emulsion of rubber-containing copolymer particles is sampled, diluted with water to a solid content of 500 ppm, and a UV 1200 V spectrophotometer. Absorbance at a wavelength of 550 nm was measured using (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.

(3) Measurement of bending strength (evaluation of toughness)
The toughness of the film was evaluated by measuring the following bending strength.
The sample film cut into a length of 110 mm and a width of 15 mm was measured in accordance with JIS P 8115 (International Organization for Standardization: ISO 5626), the number of folding resistances in the direction perpendicular to the MD direction, and the average value was shown. The test conditions are described below.
Test conditions Test machine: MIT weather resistance tester (Toyo Seiki Seisakusho Co., Ltd.)
Load: 2.45N (= 250g)
Bending angle: ± 135 °
Bending speed: 175 cpm
Specimen gripper
Tip radius: R = 0.38mm
Opening: 0.25mm
The result of the folding test is displayed with the folding strength.
Folding strength is calculated by the following formula.
Folding strength = Log n
(In the formula, n indicates the number of times the test piece reaches the damage (breaking fracture).)

(4) Measurement of film thickness The center part of each original film was measured using a micrometer (manufactured by Mitutoyo Corporation).

(5) Measurement of total light transmittance and 23 ° C. haze, 70 ° C. high temperature haze The total light transmittance and 23 ° C. haze value of each original film were measured according to JIS-K7136.
Each raw film was sandwiched between 3 mm acrylic plates, and the haze value was measured in a state kept at 70 ° C. with warm water.

(6) Surface glossiness The surface glossiness at 60 ° was measured using a gloss meter (GM-26D type manufactured by Murakami Color Research Laboratory).

(7) Surface hardness (pencil hardness)
The pencil scratch value was measured according to JIS K 5400.

(8) The film forming stability was evaluated according to the following criteria.
(Double-circle): Since fluidity | liquidity of resin is very favorable, a moldability is very favorable.
○: The moldability is good because the fluidity of the resin is good.
(Triangle | delta): Since fluidity | liquidity of resin is unstable, a moldability is not stabilized.

(9) Measurement of refractive index The average refractive index at 23 ° C. and 550 nm of a heat-resistant acrylic resin (a) press product was measured using a laser refractometer Model 2010 manufactured by Metricon.

The manufacturing method of resin used in the Example and comparative example which are mentioned later is shown.
[(1) Acrylic resin: heat-resistant acrylic resin (a), acrylic resin (d)]
(1-1) Heat-resistant acrylic resin (a-1)
In accordance with the method described in Japanese Patent Publication No. 63-1964, a heat-resistant acrylic resin (a-1), which is a methyl methacrylate-styrene-maleic anhydride copolymer, was obtained.
The composition of the obtained copolymer was 72% by mass of methyl methacrylate unit, 16% by mass of styrene unit, 12% by mass of maleic anhydride unit, the mass average molecular weight was 100,000, and the copolymer melt flow rate value (ASTM -D1238; 230 ° C., 3.8 kg load) was 2.5 g / 10 min.
The heat-resistant acrylic resin (a-1) was used in Examples 1 to 6, 8 and Comparative Examples 1 and 3-5.

(1-2) Heat-resistant acrylic resin (a-2)
By the same method as above, a heat-resistant acrylic resin (a-2) having a copolymer composition of 70% by mass of methyl methacrylate units, 16% by mass of styrene units and 14% by mass of maleic anhydride units was obtained.
The mass average molecular weight was 120,000, and the copolymer melt flow rate value (ASTM-D1238; 230 ° C., 3.8 kg load) was 1.2 g / 10 min.
The heat-resistant acrylic resin (a-2) was used in Example 7 described later.

(1-3) Acrylic resin (d-1)
By the same method as described above, an acrylic resin (d-1) having a copolymer composition of 51% by mass of methyl methacrylate units, 45% by mass of styrene units and 4% by mass of maleic anhydride units was obtained.
The weight average molecular weight was 120,000, and the copolymer melt flow rate value (ASTM-D1238; 230 ° C., 3.8 kg load) was 1.8 g / 10 min.
The acrylic resin (d-1) was used in Comparative Example 2 described later.

(1-4) Acrylic resin (d-2)
A monomer mixture consisting of 94% by weight of methyl methacrylate, 2.5% by weight of methyl acrylate, and 3.5% by weight of xylene was added to 1,1-di-t with respect to 100 parts by weight of the monomer mixture. -0.03 part by mass of butylperoxy-3,3,3-trimethylcyclohexane and 0.12 part by mass of n-octyl mercaptan were added and mixed uniformly.
This solution was continuously supplied to a sealed pressure-resistant reactor having an internal volume of 10 L, polymerized with stirring at an average temperature of 130 ° C. and an average residence time of 2 hours, and then continuously sent to a reservoir connected to the reactor, Volatiles were removed under certain conditions.
Further, it was continuously transferred to an extruder in a molten state to obtain an acrylic resin (d-2) having a copolymer composition of 98% by mass of methyl methacrylate units and 2% by mass of methyl acrylate units.
The mass average molecular weight was 102,000, and the copolymer melt flow rate value (ASTM-D1238; 230 ° C., 3.8 kg load) was 2.0 g / 10 min.
The acrylic resin (d-1) was used in Comparative Example 6 described later.

[(2) Rubber-containing copolymer particles (b)]
The abbreviations shown in the method for producing rubber-containing copolymer particles (b) 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

(2-1) Rubber-containing copolymer particles having a three-layer structure (b-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 rubber-containing copolymer particles (b-1) obtained had an average particle size of 0.1 μm.
Moreover, the refractive index difference with heat-resistant acrylic resin (a) was 0.004.

(2-2) Rubber-containing copolymer particles having a three-layer structure (b-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).
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 sodium sulfate solution for salting out and coagulation. Next, after repeating dehydration and washing, drying treatment was performed to obtain rubber-containing copolymer particles (b- 2) was obtained as a powder.
The refractive index difference from the heat-resistant acrylic resin (a) was 0.008.

(2-3) Rubber-containing copolymer particles having a three-layer structure (b-3)
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).
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 emulsified liquid is poured 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 rubber-containing copolymer (b-3) as a powder. It was.
Moreover, the refractive index difference with heat-resistant acrylic resin (a) was 0.008.

(2-4) Rubber-containing copolymer particles having a three-layer structure (c-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, 1.3 g of Rongalite was added as a reducing agent and dissolved uniformly.
As a first layer, a monomer mixture of MMA 190 g, BA 2.5 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 1360 g, St 320 g, PEGDA 40 g, ALMA 7.0 g, DPBHP 1.6 g and Rongalite 1.0 g was added dropwise over 90 minutes. The reaction was completed 40 minutes after the completion of the dropwise addition.
Next, a monomer mixture of MMA 190 g, BA 2.3 g, and DPBHP 0.2 g 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, MMA 380 g, BA 4.6 g, DPBHP 0.4 g, and n-OM 1.2 g monomer mixture was added over 10 minutes as the second layer of the third layer. 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 rubber-containing copolymer particles (c-1) obtained had an average particle size of 0.1 μm.
The refractive index difference from the heat-resistant acrylic resin (a) was 0.019.
The refractive index difference with the polymethacrylate resin was 0.001.

(2-5) Rubber-containing copolymer particles having a three-layer structure (c-2)
Ion-exchanged water 6868 mL and sodium dihexyl sulfosuccinate 13.7 g were put into a reactor with a reflux condenser with an internal volume of 10 L, and the temperature was raised to 75 ° C. under a nitrogen atmosphere while stirring at a rotational speed of 250 rpm. Was virtually absent (substantially oxygen-free).
Of the mixture (1-1) consisting of MMA 907 g, BA 33 g, HMBT 0.28 g and ALMA 0.93 g, 222 g was added all at once, and after 5 minutes, 0.22 g of ammonium persulfate was added.
After 40 minutes, the remaining 719 g of (I-1) was continuously added over 20 minutes, and the addition was continued for 60 minutes.
Next, after adding 1.01 g of ammonium persulfate, a mixture (I-2) comprising 1067 g of BA, St219 g, 0.39 g of HMBT, and 27.3 g of ALMA was continuously added over 140 minutes, and the mixture was further maintained for 180 minutes. did.
Next, after adding 0.30 g of ammonium persulfate, a mixture (I-3) composed of MMA 730 g, BA 26.5 g, HMBT 0.22 g, and n-OM 0.76 g was continuously added over 40 minutes. The temperature was raised to 95 ° C. and held for 30 minutes.
The remaining latex was put into a 3% by mass sodium sulfate warm aqueous solution, salted and coagulated, and then dried after repeated dehydration and washing to obtain rubber-containing copolymer particles (c-2).
The rubber-containing copolymer particles (c-2) obtained had an average particle size of 0.23 μm.
Moreover, the refractive index difference with heat-resistant acrylic resin (a) was 0.02.

(2-6) Rubber-containing copolymer particles having a three-layer structure (c-3)
As an emulsifier, 15 g of sodium dioctyl sulfosuccinate was added. Other conditions were polymerized by the same formulation as the above (b-1).
The rubber-containing copolymer particles (c-3) obtained had an average particle size of 0.15 μm.
The refractive index difference from the heat-resistant acrylic resin (a) was 0.004.

[Examples 1-8], [Comparative Examples 1-6]
Using a T-die mounting extruder (BT-30-C-36-L type / width 400 mm, T-die mounting / lip thickness 0.8 mm) manufactured by the Institute of Plastics Engineering, screw rotation speed, resin temperature in the cylinder of the extruder, T A raw film was obtained by adjusting the temperature of the die and performing extrusion molding.
The flow (extrusion direction) of the film was defined as the MD direction, and the direction perpendicular to the MD direction was defined as the TD direction.
In Examples 1 to 8 and Comparative Examples 3 to 6, the heat-resistant acrylic resin and various rubber-containing copolymer particles were compounded by a twin screw extruder, and the pellets were T-die extruded.
In Comparative Examples 1 and 2, extrusion molding was performed without blending the rubber-containing copolymer particles.
Table 1 below shows the copolymer composition ratio of the heat-resistant acrylic resin, the blending ratio of the rubber-containing copolymer particles, the film molding conditions, the property evaluation results, and the film property results.

In Examples 1 to 6 and 8, rubber-containing copolymer particles (b-1 to b-3) having a specific three-layer structure were blended with a heat-resistant acrylic resin having a specific copolymer composition ratio. As a result, an acrylic resin film excellent in film forming processability and film property balance was obtained. It was excellent in transparency, toughness, heat resistance, surface glossiness, and pencil hardness, and was extremely useful as a coating substitute film.
Further, in Example 7, the glass transition temperature was 135 ° C., and it was useful as a coating substitute film for applications requiring higher heat resistance.

In Comparative Example 1, since the rubber-containing copolymer particles were not mixed, the toughness was insufficient.
In Comparative Example 2, the copolymer composition ratio of the acrylic resin is outside the range of the present invention, the heat resistance is insufficient, and further, the rubber-containing copolymer particles are not mixed, so that the toughness is also insufficient. Met.
In Comparative Example 3, an increase in haze value was observed because the difference in refractive index between the heat-resistant acrylic resin and the rubber-containing copolymer particles (c-1) was large.
In Comparative Example 4, by using the rubber-containing copolymer particles (c-2) having a large average particle size, surface irregularities (external haze) occurred when the film was formed into a thin film, and the haze value of the film was Increased and surface gloss decreased.
In Comparative Example 5, the difference in refractive index from the heat-resistant acrylic resin was appropriate by using the rubber-containing copolymer particles (c-3), but the haze of the film was large because the average particle diameter was large. The value rose.
In Comparative Example 6, the copolymer composition of the acrylic resin was outside the range of the present invention, and the heat resistance of the film was insufficient.

  The coating substitute film of the present invention and the laminated molded body using the same are conventionally used for automobile interior parts such as console boxes and shift lever boxes, vehicle exterior parts such as two-wheeled cowlings, home appliances, furniture, building materials, and mobile phones. As an alternative material for coating materials that have already been painted, there is industrial applicability.

Claims (8)

Methacrylic acid ester and / or acrylic acid ester unit 40 mass% or more and 90 mass% or less, aromatic vinyl compound unit 5 mass% or more and 40 mass% or less, and compound unit 5 mass% represented by the following general formula (1) Heat-resistant acrylic resin (a) containing 30% by mass or less and 100 parts by mass,
(In the general formula (1), X represents O or N—R, O is an oxygen atom, N is a nitrogen atom, R is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a cycloalkyl group. Indicates either.)
Rubber-containing copolymer particles (b) having a multilayer structure having a refractive index difference with respect to the heat-resistant acrylic resin (a) of 0.015 or less and an average particle size of 0.04 μm or more and 0.13 μm or less: 0.1 parts by mass or more and 100 parts by mass or less,
A coating substitute film containing   2. The coating substitute according to claim 1, wherein the rubber-containing copolymer particles (b) are particles having a multilayer structure of three layers or more in which a hard layer, a soft layer, and a hard layer are formed from the inside. the film.   The coating substitute film according to claim 1 or 2, wherein the film thickness is 200 µm or less, the haze value in a 23 ° C environment is 2.0% or less, and the 60 ° surface glossiness is 120% or more.   The coating substitute film according to any one of claims 1 to 3, wherein a haze value in an environment of 70 ° C is 3.0% or less.   The paint substitute film according to any one of claims 1 to 4, wherein Tg (glass transition temperature) is 120 ° C or higher.   The coating substitute film according to any one of claims 1 to 5, wherein a printed image is formed on one side.   A laminated molded product obtained by laminating the coating substitute film according to any one of claims 1 to 6 and a base material.   The lamination according to claim 7, wherein the coating substitute film according to any one of claims 1 to 6 is subjected to a molding treatment, and then a resin is injection-molded on the coating substitute film to laminate a base material. Molded body.