JP2019189849A - Acrylic resin composition and film, and laminate - Google Patents

Abstract

To provide an acrylic resin composition that has high transparency and stress whitening resistance, and satisfies ultraviolet blocking performance and hot water resistance.SOLUTION: The present invention provides an acrylic resin composition, wherein, when the acrylic resin composition is molded into a film of 50 μm in thickness, it has a transmittance to light of 370 nm in wavelength of less than 1%, and has a tensile elasticity of 10-1,000 MPa, and the content of a triazine ultraviolet absorber (C1) is 0.1-10 mass%. There is also provided a film including the same.SELECTED DRAWING: None

Description

  The present invention relates to an acrylic resin composition, a film, and a laminate.

  Acrylic resin is excellent in transparency and weather resistance. For example, it protects the surface by bonding it to various molded products for indoor or outdoor use, such as optical parts of electrical products, automobile interior parts, signboards, building materials, etc. It is preferably used as a layer. In addition, surface treatment such as antireflection treatment and antifouling treatment is applied to the surface of the acrylic resin film, and this is bonded to the molded product to give the molded product surface functions such as antireflection and antifouling properties. You can also

  When laminating the above-mentioned acrylic resin on a base material, a decorative sheet is created by laminating the base material and the acrylic resin film and applying heat press, and bending is often performed to a shape suitable for the application. . During this bending process, the acrylic resin film may be whitened, cracked or peeled off, and so far, films having excellent whitening resistance and workability have been developed.

  For example, Patent Document 1 discloses an acrylic resin composition having high weather resistance, heat resistance, transparency, and stress whitening resistance by using a specific soft acrylic resin. Patent Document 2 discloses a laminated film having high transparency, stress whitening resistance, and chemical resistance by laminating a specific soft acrylic resin and a polyvinylidene fluoride resin.

International Publication No. 2015/156323 International Publication No. 2017/043467

  However, these soft acrylic resins have a problem of coloring in a warm water resistance test when a specific ultraviolet absorber is added. Moreover, these soft acrylic resins are likely to cause bleeding out of the ultraviolet absorber, and there are limitations on the types and amounts that can be added. Although the warm water resistance can be improved by not adding an ultraviolet absorber, since the ultraviolet shielding property is lost, there is a problem that it is difficult to use for the purpose of protecting the substrate from ultraviolet rays. Then, the objective of this invention is providing the acrylic resin composition which has high transparency and stress whitening resistance, and also satisfy | fills ultraviolet-ray shielding property and warm water resistance.

As a result of intensive studies, the present inventor has found that the above object can be achieved by combining an acrylic resin having a specific composition and a specific ultraviolet absorber, and has completed the present invention. That is, the present invention relates to the following [1] to [9].
[1] The transmittance for light having a wavelength of 370 nm when the acrylic resin composition is formed into a film having a thickness of 50 μm is less than 1%,
Tensile modulus is 10 to 1,000 MPa,
The acrylic resin composition whose content of a triazine type ultraviolet absorber (C1) is 0.1-10 mass%.
[2] The triazine-based ultraviolet absorber (C1) is represented by the structure of the following formula (1).
The acrylic resin composition according to [1].

(1)
[In formula (1), G1 is hydrogen; C1-C18 alkyl; -OH, C2-C18 alkenyloxy, -C (O) OL1 and -OC (O) L2 (wherein L1 and L2 are independently C1-C18 alkyl substituted by 1, 2 or 3 groups selected from the group consisting of: C1-C18 alkyl; C3-C50 alkyl interrupted by oxygen; or C3-C50 interrupted by oxygen Hydroxyalkyl, G2, G3, G4 and G5 are independently hydrogen; C1-C18 alkyl; phenyl; or phenyl substituted by 1, 2 or 3 C1-C4 alkyl]

[3] The content of the triazine-based ultraviolet absorber (C1) is less than 2% by mass. [1]
Or the acrylic resin composition as described in [2].
[4] The content of the benzotriazole ultraviolet absorber is less than 0.1% by mass, [1] to [1]
The acrylic resin composition according to any one of [3].
[5] An acrylic resin film comprising the acrylic resin composition according to any one of [1] to [4].
[6] A matte film comprising the acrylic resin film according to [5].
[7] Resin layer (I) comprising the acrylic resin composition according to any one of [1] to [4]
And the acrylic resin laminated | multilayer film which has resin layer (II) which consists of a fluorine resin composition (B).
[8] A protective film comprising the film according to any one of [5] to [7].
[9] A protective film for a decorative steel sheet using the film according to any one of [5] to [7].

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the acrylic resin composition which has high transparency and stress whitening-proof property, and also satisfy | fills ultraviolet-ray shielding property and warm water resistance.

[Acrylic resin composition (A)]
The acrylic resin composition (A) of the present invention contains at least a triazine-based ultraviolet absorber (C1). For example, a core-shell rubber (A1), a thermoplastic polymer (A2), a triazine-based ultraviolet absorber (C1), and an additive (C2) can be contained. Particularly, the acrylic resin composition (A) contains 30 to 100% by mass of (A1), 0 to 70% by mass of (A2), and further 0.1 to 10% by mass of triazine-based ultraviolet absorber (C1). %, And additive (C2) is preferably contained in an amount of 0 to 20% by mass. When the content of the core-shell rubber (A1) is 30% by mass or more, the stress whitening resistance of the resin composition of the present invention is good. Moreover, the cracking at the time of a bending and extending | stretching process is prevented by improving a softness | flexibility, and workability improves. Further, when the content of the triazine-based ultraviolet absorber is 0.1% by mass or more, the ultraviolet ray shielding properties of the acrylic resin composition and the film of the present invention are good, and the weather resistance and the protective ability of the base material are good. .

  The acrylic resin composition (A) preferably contains 50 to 100% by mass of (A1), 0 to 50% by mass of (A2), 90 to 100% by mass of (A1), and 0 to (A2). It is more preferable that 10% by mass is contained, and it is particularly preferable that 95 to 100% by mass of (A1) and 0 to 5% by mass of (A2).

  Furthermore, the acrylic resin composition (A) needs to contain 0.1 to 10% by mass of the triazine-based ultraviolet absorber (C1). The content is preferably 1 to 3% by mass, more preferably 1.5 to 2.5% by mass, and particularly preferably 1.7% by mass or more and less than 2.0% by mass.

  Further, the acrylic resin composition (A) preferably contains 0.1 to 10% by mass of the additive (C2), more preferably 0.2 to 2% by mass, and further preferably 0.3 to 1%. It is particularly preferable to contain it by mass%. The acrylic resin composition (A) may not contain the thermoplastic polymer (A2) and the additive (C2).

  The gel fraction of the acrylic resin composition (A) is preferably 30% by mass or more, more preferably 40 to 80% by mass, still more preferably 50 to 75% by mass, and particularly preferably 60 to 70% by mass. The higher the gel fraction, the better the flexibility of the acrylic resin composition (A) and the better the stress whitening resistance. Moreover, the fluidity | liquidity of an acrylic resin composition (A) improves, and a moldability becomes favorable, so that a gel fraction is low. The gel fraction is a value measured by the method described later.

  The acrylic resin composition (A) needs to have a transmittance of less than 1% when irradiated with light having a wavelength of 370 nm when molded to a thickness of 50 μm. If the transmittance is less than 1%, the ultraviolet ray shielding property is good, the weather resistance of the acrylic resin composition (A) is good, and the protective ability of the substrate on which the acrylic resin composition (A) is laminated Becomes better. When the acrylic resin composition (A) is molded to a thickness of 50 μm, the transmittance at 370 nm is more preferably from 0.01 to 0.5%, still more preferably from 0.02 to 0.3%.

  The elastic modulus of the acrylic resin composition (A) needs to be 10 to 1,000 MPa. The elastic modulus of the acrylic resin composition is preferably 100 to 800 MPa, and more preferably 300 to 600 MPa. When the elastic modulus is 10 MPa or more, blocking between the films made of the acrylic resin composition (A) is suppressed, and appropriate rigidity is imparted to the film, so that handleability is improved. When the elastic modulus is 1,000 MPa or less, the flexibility of the acrylic resin composition (A) is improved and the stress whitening resistance is improved. The elastic modulus is a value measured by a method described later.

  The fracture elongation of the acrylic resin composition (A) is preferably 50% or more, more preferably 80% or more, still more preferably 100% or more, and particularly preferably 120% or more. If the fracture elongation is 50% or more, the film made of the acrylic resin composition (A) of the present invention is hardly cracked or peeled during bending and stretching, and the workability is improved.

  As for the glass transition temperature (henceforth, Tg) of an acrylic resin composition (A), 70-120 degreeC is preferable. If the acrylic resin composition (A) has a Tg of 70 ° C. or higher, the molded article made of the acrylic resin composition (A) has good heat resistance and rigidity. If the Tg is 120 ° C. or lower, the acrylic resin composition. The fluidity of (A) is improved, the moldability is improved, the flexibility is improved, and the stress whitening resistance is also improved. The Tg of the acrylic resin composition (A) is more preferably 80 to 110 ° C, further preferably 95 to 100 ° C.

The acrylic resin composition (A) preferably has a melt flow rate (hereinafter referred to as MFR) of 1 to 20 g / 10 min measured at a temperature of 230 ° C. and a load of 49 N, more preferably 2 to 10 g / 10 min. 3 to 6 g / 10 min is more preferable. If the MFR of the acrylic resin composition (A) is 1 g / 10 min or more, the moldability is excellent, and if it is 20 g / 10 min or less, the process stability is excellent.

[Core shell rubber (A1)]
The core-shell rubber (A1) is composed of one or more monomers selected from alkyl acrylate (a1) having an alkyl group having 1 to 8 carbon atoms and alkyl methacrylate (a2) having an alkyl group having 1 to 4 carbon atoms, In the presence of an elastic polymer (A1a) obtained by polymerizing a monomer (a) containing a crosslinkable monomer (a4), an alkyl methacrylate (b1) having an alkyl group having 1 to 4 carbon atoms is obtained. It is obtained by polymerizing the monomer (b) containing it.

  In the alkyl acrylate (a1) having an alkyl group having 1 to 8 carbon atoms, the alkyl group may be linear or branched. Specific examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These may be used alone or in combination of two or more. In this, the alkyl acrylate with a low glass transition temperature (henceforth Tg) of a homopolymer is preferable, and n-butyl acrylate is more preferable. If Tg is low, the elastic polymer (A1a) has good flexibility and can be easily molded.

  In the alkyl methacrylate (a2) having an alkyl group having 1 to 4 carbon atoms, the alkyl group may be linear or branched. Specific examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. These may be used alone or in combination of two or more.

  Only one of alkyl acrylate (a1) and alkyl methacrylate (a2) may be used, or a combination of both may be used. In 100% by mass of the monomer (a) used as a raw material for the elastic polymer (A1a), the ratio of the alkyl acrylate (a1) is such that the flexibility of the resulting acrylic resin composition (A) becomes good. It is preferably at least mass%, more preferably at least 60 mass%, even more preferably at least 90 mass%, particularly preferably at least 93 mass%.

  As the monomer (a) used as a raw material for the elastic polymer (A1a), other vinyl monomers (a3) other than the alkyl acrylate (a1) and the alkyl methacrylate (a2) can be used together. Other vinyl monomers (a3) include, for example, acrylate monomers having an alkyl group having 9 or more carbon atoms, such as alkyl acrylate, alkoxy acrylate, cyanoethyl acrylate; acrylamide, acrylic acid, methacrylic acid, styrene, alkyl substitution Examples include styrene, acrylonitrile, and methacrylonitrile.

  The crosslinkable monomer (a4) forms a cross-linked structure with the alkyl acrylate (a1) and / or the alkyl methacrylate (a2), imparts rubber elasticity to the polymer, and is between the hard polymer (A1b). It is a component that forms a crosslink. Among these, a graft crossing agent having a function of causing graft crossing is preferable. As what has such a function, allyl, methallyl, or crotyl ester of copolymerizable (alpha), (beta)-unsaturated carboxylic acid or dicarboxylic acid is mentioned, for example. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid. Among them, allyl methacrylate has an excellent effect. In addition, triallyl cyanurate and triallyl isocyanurate are also effective.

Graft-crossing agents are chemically bonded, primarily because the conjugated unsaturated bond of the ester reacts much faster than allyl, methallyl or crotyl groups. In the meantime, a substantial part of the allyl group, methallyl group or crotyl group works effectively during the polymerization of the next layer polymer, and gives a graft bond between the adjacent two layers.

  The crosslinkable monomer (a4) is not limited to a monomer that imparts rubber elasticity to the molded product obtained as described above or causes crossover of the graft. It may be a monomer. Examples thereof include alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate; polyvinylbenzene such as divinylbenzene and trivinylbenzene.

  As described above, various compounds can be selected as the crosslinkable monomer (a4). However, in order to suitably exhibit the stress whitening resistance, it is preferable to use a graft cross-linking agent such as allyl methacrylate. More preferably, only the graft crossing agent is used as the monomer (a4).

  The total amount of alkyl acrylate (a1) and alkyl methacrylate (a2) in the total 100% by mass of the above monomers (a1) to (a4) is 80 to 100% by mass in terms of weather resistance and the like. The amount of (a3) is preferably 0 to 20% by mass. From the viewpoint of stress whitening resistance, the content ratio of the monomer (a1) unit / monomer (a2) unit is preferably 50/50 to 100/0 (mass ratio), and 90/10 to 10/10. 95/5 is more preferable. From the viewpoint of stress whitening resistance, the amount of the monomer (a3) is more preferably 0 to 12% by mass.

The amount of the crosslinkable monomer (a4) is 100% by mass in total of the monomers (a1) to (a4).
0.4-2.0 mass% is preferable, 0.6-1.8 mass% is more preferable, 1.2-
1.7 mass% is still more preferable. If this amount is 0.4% by mass or more, crosslinking between the elastic polymer (A1a) and the hard polymer (A1b) becomes stable, and sufficient transparency is exhibited. Moreover, rubber elasticity can be improved more and the impact resistance of the molded object which consists of an acrylic resin composition (A) obtained increases. Conversely, if it is 2.0 mass% or less, bridge | crosslinking can be controlled moderately and the softness | flexibility of the molded object which consists of an acrylic resin composition (A) obtained will express suitably.

  The elastic polymer (A1a) may be polymerized in two or more stages. In that case, monomer mixtures having different compositions may be polymerized. By polymerizing in two or more stages, it becomes easy to control the particle diameter of the finally obtained rubber-containing polymer (A1).

  For example, when the elastic polymer (A1a) is polymerized in two stages, the first elastic polymer (A1a-1) and the second elastic polymer (A1a-2) are grafted between two layers by a graft crossing agent. It is preferable to have a bond.

  If the elastic polymer (A1a) is polymerized in two or more stages and has a graft bond between two adjacent layers, the particle size of the rubber-containing polymer (A1) can be easily controlled, and the resistance Stress whitening can be suitably expressed.

  In the elastic polymer (A1a), the content of the graft crossing agent unit in 100% by mass of the elastic polymer (A1a) is preferably 1.2% by mass or more, and more preferably 1.5% by mass or more. preferable. If the content of the graft crossing agent unit is 1.2% by mass or more, the interlayer between the first elastic polymer (A1a-1) and the second elastic polymer (A1a-2), or the elastic polymer (A1a) And the cross-linking between the layers of the hard polymer (A1b) becomes stable, and stress whitening resistance is suitably developed.

  The elastic polymer (A1a) is obtained by a polymerization method such as emulsion polymerization or suspension polymerization. In the case of emulsion polymerization, an emulsifier, a polymerization initiator, and a chain transfer agent can be used.

  As the emulsifier, an anionic, cationic or nonionic surfactant is used, and an anionic surfactant is particularly preferable.

  Specific examples of the anionic surfactant include rosin acid soap, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroylsarcosate, dialkenyl succinate, etc .; sodium lauryl sulfate, etc. Sulfate salts such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate, and the like; and phosphate esters such as polyoxyethylene alkylphenylether sodium phosphate. Especially, since the fluidity | liquidity of a rubber containing polymer (A1) becomes favorable, an alkyl sulfonate is preferable and a dioctyl sodium sulfosuccinate is especially preferable.

  Examples of the method for preparing the emulsion include a method of adding a surfactant after charging the monomer mixture in water, a method of charging the monomer mixture after charging the surfactant in water, and a monomer An example is a method in which water is added after a surfactant is charged into the mixture. Among these, a method of charging the surfactant after charging the monomer mixture into water and a method of charging the monomer mixture after charging the surfactant into water are preferable.

  Specific examples of the polymerization initiator include persulfates such as potassium persulfate and sodium persulfate; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide and benzoyl peroxide; azobisisobutyronitrile. Azo compounds such as: redox initiators in which these persulfates or organic peroxides are combined with a reducing agent. Among these, a redox initiator is preferable, and a sulfoxylate initiator combined with ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate, and hydroperoxide is more preferable. The polymerization initiator can be added to one or both of the aqueous phase and the monomer phase.

The amount of the polymerization initiator is preferably 0.05 to 1.0 part by mass and more preferably 0.1 to 0.6 part by mass with respect to 100 parts by mass in total of the monomers (a1) to (a4). . If the amount of the polymerization initiator is 0.05 parts by mass or more, the mechanical strength of the molded body containing the core-shell rubber (A1) will be good. Moreover, if it is 1.0 mass part or less, fluidity | liquidity will become favorable and the moldability at the time of melt-extrusion and shape | molding an acrylic resin composition (A) will become favorable.

  Specific examples of the chain transfer agent include C 2-20 alkyl mercaptan, mercapto acids, thiophenol, and carbon tetrachloride. The chain transfer agent is preferably mixed during the polymerization of the hard polymer (A1b), and n-octyl mercaptan is preferable.

  Although superposition | polymerization temperature changes with kinds and quantity of a polymerization initiator, Preferably it is 40-120 degreeC, More preferably, it is 60-95 degreeC.

  Prior to the polymerization of the elastic polymer (A1a), the core part having a Tg exceeding 0 ° C. may be polymerized. The core is preferably 0 to 10% by mass in the core-shell rubber (A1) from the viewpoint of the stability of polymer particle size generation. The core is an alkyl acrylate (a1) having an alkyl group having 1 to 8 carbon atoms, 10 to 50% by mass, an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (a2), 20 to 70% by mass, and other vinyl monomers Polymerization of monomer (a) containing 0 to 10% by mass of body (a3) and 0.1 to 10% by mass of crosslinkable monomer (a4) (total of (a1) to (a4) is 100% by mass) What is obtained is preferable.

The core-shell rubber (A1) is obtained by polymerizing the monomer (b) containing an alkyl methacrylate (b1) having an alkyl group having 1 to 4 carbon atoms in the presence of the above-described elastic polymer (A1a). . The monomer (b) is polymerized to form a hard part (A1b). Specific examples of the alkyl methacrylate (b1) include the same as the specific examples of the alkyl methacrylate (a2). They may be used alone or in combination of two or more.

  As the monomer (b), other monomers (b2) other than the alkyl methacrylate (b1) can also be used. Specific examples of the other monomer (b2) include the same examples as the specific examples of the alkyl acrylate (a1) and the other vinyl monomer (a3). They may be used alone or in combination of two or more.

  In 100% by mass of the monomer (b), the content of the alkyl methacrylate (b1) is preferably 70% by mass or more, and more preferably 85% by mass or more. Thereby, Tg of a hard part (B2) can be made high moderately.

  The monomer (b) may be polymerized in two or more stages. In that case, monomer mixtures having different compositions may be polymerized. In the polymerization reaction of the monomer (b), after the polymerization reaction of the elastic polymer (A1a) is completed, the obtained polymerization solution is used as it is, and then the monomer (b) is added and polymerization is continued. preferable. Specific examples of the emulsifier, the polymerization initiator, and the chain transfer agent in this polymerization are the same as the specific examples in the polymerization of the elastic polymer (A1a).

  0.1-2 mass parts is preferable with respect to 100 mass parts of monomers (b), and, as for the quantity of a chain transfer agent, 0.2-1 mass parts is more preferable. When the amount of the chain transfer agent is 0.1 parts by mass or more, the flexibility of the molded body is increased. Moreover, if it is 2 mass parts or less, the mechanical strength of a molded object will become high.

The Tg of the elastic polymer (A1a) is preferably 0 ° C. or lower, more preferably −30 ° C. or lower,
More preferably, it is −40 ° C. or lower. If Tg is 0 ° C. or less, the molded body made of the acrylic resin composition (A) has preferable impact resistance. This Tg is a value measured and calculated as follows using a dynamic viscoelasticity measuring apparatus. A test piece was formed into a sheet having a width of 6 mm and a thickness of 1 mm, and using a dynamic viscoelasticity measuring device, the distance between initial chucks was 2 cm, the measurement frequency was 0.1 Hz, and the measurement temperature range was −90 in accordance with ISO 6721-4. The storage elastic modulus (E ′) and loss elastic modulus (E ″) were measured in a tensile mode under the conditions of ˜150 ° C., a temperature rising rate of 2 ° C./min, and a nitrogen stream of 200 mL / min, and tan δ = E ′ The value of tan δ (loss tangent) at each temperature is calculated according to the equation of “/ E”. Next, when the value of tan δ is plotted against temperature, two or more peaks appear. Of these, the temperature corresponding to the peak appearing at the lowest temperature is defined as Tg of the elastic polymer (A1a).

  The Tg of the hard part (A1b) is preferably 70 to 120 ° C. If the Tg of the hard part (A1b) is 70 ° C. or higher, the heat resistance and rigidity of the molded body made of the acrylic resin composition (A) will be good, and if the Tg is 120 ° C. or lower, the acrylic resin composition (A ) Is improved, the moldability is improved, the flexibility is improved, and the stress whitening resistance is also improved. The Tg of the hard part (A1b) is more preferably 80 to 110 ° C, and still more preferably 95 to 100 ° C. Tg of the hard part (A1b) is a temperature corresponding to a peak appearing at the highest temperature in the dynamic viscoelasticity measurement similar to the method of measuring the Tg of the elastic polymer (A1a).

  In addition, after completion of the polymerization reaction of the elastic polymer (A1a), before the polymerization of the monomer (b), from the composition of the monomer constituting the elastic polymer (A1a), an alkyl having 1 to 8 carbon atoms is obtained. A monomer having a composition in which the ratio of the alkyl acrylate having a group (a1) is gradually reduced and the ratio of the alkyl methacrylate having a C 1-4 alkyl group (a2) is gradually increased is sequentially polymerized. A part (A1c) can also be formed.

  30 mass% or more is preferable, as for the ratio of the elastic polymer (A1a) in 100 mass% of core-shell rubber (A1), 40-70 mass% is more preferable, and 50-60 mass% is still more preferable. If the ratio of the elastic polymer (A1a) is 30% by mass or more, the mechanical strength and flexibility of the resulting acrylic resin composition (A) and the molded body are improved, and whitening when cracked or bent can be suppressed. . Moreover, whitening, peeling, and breakage can be suppressed when the substrate is laminated and bent. If the ratio of an elastic polymer (A1a) is 70 mass% or less, it will be excellent in the thickness precision at the time of shape | molding the acrylic resin composition (A) obtained to a film, and the productivity at the time of shaping | molding will not fall.

  70 mass% or less is preferable, as for the ratio of the hard part (A1b) in 100 mass% of core-shell rubber (A1), 30-60 mass% is more preferable, and 40-50 mass% is still more preferable. If the ratio of a hard part (A1b) is 30 mass% or more, the fluidity | liquidity of the acrylic resin composition (A) obtained will improve and a moldability will become favorable. If it is 70 mass% or less, a softness | flexibility will improve and stress whitening resistance will become favorable.

  When the emulsion polymerization method is used, the core-shell rubber (A1) is recovered as a powder from the latex after completion of the polymerization reaction. Examples of the method for recovering as powder include coagulation or salting out by bringing latex into contact with a coagulant, solid-liquid separation, washing with water 1 to 100 times the mass of the polymer, and dehydration such as filtration. A wet powder is obtained by the treatment, and the wet powder is further dried by a hot air dryer such as a press dehydrator or a fluid dryer. In addition, the latex may be directly dried by a spray drying method. The drying temperature and drying time of the polymer can be appropriately determined depending on the type of polymer.

  Specific examples of the coagulant include organic salts such as sodium acetate, calcium acetate, potassium formate and calcium formate; inorganic salts such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride and sodium sulfate. Of these, calcium salts such as calcium acetate and calcium chloride are preferable. In particular, calcium acetate is more preferable from the viewpoint of the hot water whitening resistance of the molded body and the low moisture content of the recovered powder. One coagulant may be used alone, or two or more coagulants may be used in combination.

  The coagulant is usually used as an aqueous solution. The concentration of the aqueous solution of the coagulant, preferably calcium acetate, is preferably 0.1% by mass or more, and more preferably 1% by mass or more from the viewpoint that the acrylic resin composition can be stably coagulated and recovered. Further, the concentration of the aqueous solution of calcium acetate is preferably 20% by mass or less from the viewpoint that the amount of the coagulant remaining in the collected powder is small, and particularly the performance such as hot water whitening resistance and colorability is hardly deteriorated. The mass% or less is more preferable. When the concentration of calcium acetate exceeds 20% by mass, calcium acetate may precipitate due to saturation at 10 ° C. or less.

  Examples of the method of bringing the latex into contact with the coagulant include, for example, a method in which the aqueous solution of the coagulant is stirred and the latex is continuously added to the coagulant and stirring is continued for a certain period of time. There is a method in which a mixture containing solidified powder and water is continuously extracted from the container by continuously injecting into a container with a stirrer at a ratio of The amount of the aqueous solution of the coagulant is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the latex. The temperature of the coagulation step is preferably 30 to 100 ° C. from the viewpoint of blocking the obtained coagulated powder.

The weight-average molecular weight (Mw) of the acetone-soluble component of the core-shell rubber (A1) is preferably 25,000 to 70,000, more preferably 30,000 to 50,000, and even more preferably 35,000 to 40,000. . If Mw is 25,000 or more, the mechanical strength is improved and cracks during molding can be suppressed. Moreover, the fracture | rupture and whitening at the time of a bending process can be suppressed.
If Mw is 70,000 or less, the fluidity of the resulting resin composition is improved, and the processability during melt molding is excellent. Moreover, after bonding the obtained film to base materials, such as a steel plate, when bending it, whitening does not generate | occur | produce in a curved part and the external appearance of the various members obtained becomes favorable. This Mw
Is a value measured by the method described later.

  Mw of the acetone soluble part of the core-shell rubber (A1) can be adjusted by appropriately changing the amount of the chain transfer agent during the polymerization. The chain transfer agent is preferably mixed during the polymerization of the hard polymer (A1b).

[Thermoplastic polymer (A2)]
The thermoplastic polymer (A2) is a thermoplastic polymer other than the core-shell rubber (A1), and is preferably a polymer obtained by polymerizing a monomer mainly composed of an alkyl methacrylate. Examples of the thermoplastic polymer (A2) include thermoplastic polymers, polymer processing aids, and polymer matting agents described in International Publication No. 2014/192708. As the polymer matting agent, a polymer having a hydroxyl group described in JP-A No. 2003-342389 is preferable. The addition amount of the polymer matting agent can be appropriately set according to the required glossiness. Of course, if a high gloss level is required, a matting agent may not be included. When low gloss is required, the amount of matting agent added is
1-30 mass% is preferable, 5-20 mass% is more preferable, and 10-15 mass% is still more preferable. The greater the amount of matting agent added, the lower the glossiness and the better matte appearance. Further, as the amount of the matting agent added is smaller, the flexibility of the acrylic resin composition (A) is not impaired, the stress whitening resistance is improved, and the hot water whitening resistance is further improved.

[Triazine UV absorber (C1)]
The triazine ultraviolet absorber (C1) is a compound having a triazine skeleton in the molecular structure. (C1) preferably has the structure of formula (1) or formula (2), more preferably has at least the structure of formula (1), and has the structures of formula (1) and formula (2). More preferably, the compounds are used in combination. In addition, (C1) may include a compound having a triazine skeleton other than the formulas (1) and (2).

(1)
Wherein Q 1, Q 2, Q 3 and Q 4 are independently hydrogen; C 1 -C 18 alkyl; —OH, C 2 -C 18 alkenyloxy, —C (O) OY 1 and —OC (O) Y 2 (where Y1 and Y2 are independently C1-C18 alkyl) C1-C18 alkyl substituted by 1, 2 or 3 groups selected from the group consisting of: C3-C50 alkyl interrupted by oxygen; or oxygen Are C3-C50 hydroxyalkyl interrupted by R14, R15 and R16, independently of one another, are hydrogen or C1-C18 alkyl]

(2)
[Wherein G1 is hydrogen; C1-C18 alkyl; —OH, C2-C18 alkenyloxy, —C (O) OL1 and —OC (O) L2 (wherein L1 and L2 are independently C1— C1-C18 alkyl substituted by 1, 2 or 3 groups selected from the group consisting of: C18 alkyl; C3-C50 alkyl interrupted by oxygen; or C3-C50 hydroxyalkyl interrupted by oxygen And G2, G3, G4 and G5 are independently hydrogen; C1-C18 alkyl; phenyl; or phenyl substituted by 1, 2 or 3 C1-C4 alkyl]

  Among the compounds having the structure of the formula (1), the structure of the formula (3) is more preferable. As a compound having a structure of the formula (3), for example, “Tinuvin 460” (trade name, manufactured by BASF) can be mentioned as a commercial product.

(3)

  Among the compounds having the structure of the formula (2), the structure of the formula (4) is more preferable. As a compound having a structure of the formula (4), for example, “Tinuvin 1577” (trade name, manufactured by BASF) is mentioned as a commercially available product.

(4)

  When (C1) has the structure of the formula (1) or the formula (2), the bleed out is suppressed and the appearance of the molded product becomes good. Also, no coloration occurs in the hot water test, and the durability is excellent. In particular, the compound having the structure of the formula (1) has a high absorbance even in the near ultraviolet region of 370 nm and is excellent in ultraviolet shielding properties.

[Additive (C2)]
The additive (C2) is a compound other than the core-shell rubber (A1), the thermoplastic polymer (A2), and the triazine-based ultraviolet absorber (C1). For example, the additive, the lubricant, the processing aid, the plasticizer, Examples include impact improvers, foaming agents, fillers, colorants, and UV absorbers other than triazines.

  For example, the additive (C1) is preferably an ultraviolet absorber from the viewpoint of imparting weather resistance to protect the substrate. The molecular weight of the ultraviolet absorber is preferably 300 or more, and more preferably 400 or more. When the molecular weight is 300 or more, the ultraviolet absorber is less likely to volatilize during vacuum molding or pressure molding in an injection mold, and mold contamination is less likely to occur. Although the kind of ultraviolet absorber is not specifically limited, The ultraviolet absorber of molecular weight 400 or more is preferable.

  However, among the ultraviolet absorbers, it is preferable not to add benzotriazole-based ultraviolet absorbers because they tend to cause deterioration in appearance due to bleed out and coloring during a hot water test. Examples of the benzotriazole ultraviolet absorber that easily causes bleed out and hot water coloring include “ADEKA STAB LA-31” (trade name, manufactured by ADEKA Corporation).

  From the viewpoint of further improving the weather resistance, it is preferable to use a radical scavenger such as a hindered amine light stabilizer in combination with the ultraviolet absorber. As the radical scavenger, commercially available products include, for example, “ADK STAB LA-57”, “ADK STAB LA-62”, “ADK STAB LA-67”, “ADK STAB LA-63”, “ADK STAB LA-68” (any of the above) "Sanol LS-770", "Sanol LS-765", "Sanol LS-292", "Sanol LS-2626", "Sanol LS-1114", "Sanol LS-" 744 "(all are trade names, manufactured by Sankyo Lifetech Co., Ltd.). These may be used alone or in combination of two or more. The addition amount of the radical scavenger is preferably 0 to 10% by mass, more preferably 0.2 to 5% by mass from the viewpoint of bleed-out resistance.

  Moreover, it is preferable that an additive (C2) is a mold release agent from a viewpoint of preventing sticking with a press board at the time of producing a laminated board by a press. Examples of the release agent include silicone compounds, fluorine compounds, alkyl alcohols, and alkyl carboxylic acids. Of these, alkylcarboxylic acids are preferred from the standpoint of availability and economy. Examples of the alkylcarboxylic acid used as the release agent include linoleic acid, vaccenic acid, stearic acid, oleic acid, margaric acid, palmitoleic acid, palmitic acid, and pentadecylic acid. These may be used alone or in combination of two or more.

[Acrylic resin film (I)]
The acrylic resin film (I) of the present invention comprises an acrylic resin composition (A). Although the thickness of a film is not specifically limited, 10-500 micrometers is preferable, 20-200 micrometers is more preferable, 30-100 micrometers is still more preferable, 40-60 micrometers is especially preferable. If thickness is 10 micrometers or more, moderate rigidity will be provided to a film and handling property will become favorable. In addition, weather resistance and ultraviolet shielding properties are improved. On the other hand, if thickness is 500 micrometers or less, the softness | flexibility of a film will improve and lamination property and secondary processability will become favorable. Further, it is economically advantageous in terms of mass per unit area. Further, the film forming property is stabilized, and the production of the film becomes easy.

The surface appearance of the acrylic resin film (I) of the present invention is not particularly limited, and can be appropriately processed into the required surface appearance. Among these, a matte appearance is preferable from the viewpoint of design properties. In the case of a matte appearance, the acrylic resin film (I) has a 60-degree glossiness of 5 to 5.
70% is preferable, 5 to 50% is more preferable, 5 to 30% is further preferable, and 10 to 20% is particularly preferable. The 60 degree glossiness is a value measured by a method described later.

  The total light transmittance of the acrylic resin film (I) is preferably 80% or more, more preferably 83% or more, still more preferably 85% or more, and particularly preferably 90% or more. When the total light transmittance is 80% or more, the decorative layer printed on the film is beautiful when viewed from the surface on which the decorative layer is not printed, and is excellent in design.

  The acrylic resin film (I) according to the present invention preferably has a transmittance at 370 nm of less than 1%, more preferably less than 0.5%, and even more preferably less than 0.2%. . If the transmittance at 370 nm is less than 1%, for example, it is possible to protect the decorative layer and the base resin that are the base when used for decorative plate protection from deterioration due to ultraviolet rays. An excellent decorative board can be obtained.

The acrylic resin film (I) according to the present invention preferably has a haze value of 20 or less,
It is more preferably 5 or less, further preferably 2 or less, and particularly preferably 1 or less. If the haze value is 20 or less, for example, the pattern of the decorative layer serving as the foundation does not become fogged when used for decorative plate protection and overlay applications, and a decorative plate with excellent design can be obtained. In addition, since the external haze derived from the surface unevenness among the haze values of the laminated film alone becomes substantially zero after lamination with the base material, the appearance after lamination with the base material strongly depends on the internal haze value.

  The laminated film according to the present invention has an internal haze value of preferably 5 or less, more preferably 1 or less, and most preferably 0.5 or less.

  The acrylic resin film (I) according to the present invention preferably has a yellowness of 10 or less, more preferably 5 or less, and particularly preferably 2 or less. If the yellowness is 10 or less, for example, when used for decorative board protection and overlay applications, the pattern of the decorative layer that is the base does not appear discolored, and a decorative board with excellent design is obtained. Can do.

The elastic modulus of the acrylic resin film (I) is preferably 10 to 1,000 MPa, more preferably 100 to 800 MPa, and particularly preferably 300 to 600 MPa. When the elastic modulus is 10 MPa or more, blocking between the films made of the acrylic resin composition (A) is suppressed, and appropriate rigidity is imparted to the film, so that handleability is improved. When the elastic modulus is 1,000 MPa or less, the flexibility of the acrylic resin composition (A) is improved and the stress whitening resistance is improved. The elastic modulus is a value measured by a method described later.

  The breaking elongation of the acrylic resin film (I) is preferably 50% or more, more preferably 80% or more, still more preferably 100% or more, and particularly preferably 120% or more. If the breaking elongation is 50% or more, cracking and peeling are hardly caused during the bending and stretching of the film, and the workability is improved.

  The value of ΔYI of the acrylic resin film (I) before and after the hot water test is preferably 30 or less, more preferably 10 or less, and particularly preferably 5 or less. If ΔYI before and after the hot water test is 30 or less, the pattern of the base makeup layer will not appear discolored even when used in an environment in contact with warm water, and a decorative board with excellent design can be obtained. it can. Note that ΔYI before and after the hot water test is a value obtained by performing a test under the conditions described later.

  As a method for producing the acrylic resin film (I), it is preferable to use a melt extrusion method using a T die from the viewpoint of productivity and film thickness stability.

[Acrylic resin laminated film]
You may laminate | stack resin layer (II) which consists of a fluorine-type resin composition (B) with respect to resin layer (I) which is acrylic resin film (I). The laminated film can have a two-layer structure including a resin layer (I) and a resin layer (II), or a three-layer structure in which the resin layer (II) is present on both sides of the resin layer (I). In the laminated film, the ratio of the resin layer (I) / resin layer (II) thickness is preferably 50 to 95/5 to 50, more preferably 70 to 95/5 to 30, and 85 More preferably, it is -95 / 5-15. The higher the ratio of the resin layer (I), the more advantageous in terms of weather resistance, transparency, ultraviolet shielding properties, and surface hardness. The higher the ratio of the resin layer (II), the better the chemical resistance, toughness, and water resistance. This is advantageous.

The thickness of the laminated film is not particularly limited, but preferably 10 to 500 μm.
200 micrometers is more preferable, 30-100 micrometers is still more preferable, and 40-60 micrometers is especially preferable. If thickness is 10 micrometers or more, moderate rigidity will be provided to a film and handling property will become favorable. In addition, weather resistance and ultraviolet shielding properties are improved. On the other hand, if thickness is 500 micrometers or less, the softness | flexibility of a film will improve and lamination property and secondary processability will become favorable. Further, it is economically advantageous in terms of mass per unit area. Further, the film forming property is stabilized, and the production of the film becomes easy.

  When the laminated film of the present invention is used by being attached to a substrate, it is preferable from the viewpoint of chemical resistance and weather resistance that the resin layer (II) made of the fluororesin composition (B) is resurfaced.

[Fluorine-based resin composition (B)]
The fluororesin composition (B) contains at least the fluororesin (B1), and can contain, for example, a fluororesin (B1), a thermoplastic polymer (B2), and an additive (C3).

[Fluorine resin (B1)]
The fluorine resin (B1) is preferably a vinylidene fluoride resin. Examples of the vinylidene fluoride resin include polyvinylidene fluoride and copolymers such as vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene. Among these, polyvinylidene fluoride homopolymer (PVDF) is more preferable from the viewpoint of chemical resistance. A fluorine-type resin (B1) may be used individually by 1 type, and may use 2 or more types together.

  The mass average molecular weight (Mw) of the fluororesin (B1) is preferably 100,000 or more from the viewpoint of chemical resistance, and preferably 300,000 or less from the viewpoint of film forming properties.

  The fluororesin (B1) preferably has a high crystal melting point. Specifically, 150 ° C. or higher is preferable from the viewpoint of heat resistance, and 160 ° C. or higher is more preferable. The upper limit of the crystal melting point is preferably about 175 ° C. which is equal to the crystal melting point of polyvinylidene fluoride from the viewpoint of heat resistance. “Crystal melting point” means JIS K7121, 3. It means “melting peak temperature” measured according to the method described in (2).

As a commercially available product of the fluororesin (B1), for example, “Kynar 720” (trade name, manufactured by Arkema Co., Ltd., content of vinylidene fluoride: 100% by mass, crystal melting point: 169 ° C.),
“Kynar 710” (trade name, manufactured by Arkema Co., Ltd., vinylidene fluoride content: 100 mass%, crystalline melting point: 169 ° C.), “KFT # 850” (trade name, manufactured by Kureha Co., Ltd., vinylidene fluoride) Content: 100% by mass, crystalline melting point: 173 ° C.), “Solef 1006” (trade name, manufactured by Solvay Specialty Polymers, Inc., content of vinylidene fluoride: 100% by mass, crystalline melting point: 174 ° C.), “Solef 1008” (Trade name, manufactured by Solvay Specialty Polymers, Inc., content of vinylidene fluoride: 100% by mass, crystal melting point: 174 ° C.).

  From the viewpoint of stability during film production, it is preferable that the fluororesin (B1) is used in combination with the fluororesin (B1a) and the fluororesin (B1b). In the fluororesin (B1a), the MFR measured under the conditions of a temperature of 230 ° C. and a load of 49 N is preferably 15 to 30 g / 10 min, more preferably 18 to 30 g / 10 min, and still more preferably 20 to 30 g / 10 min. . If the MFR of the fluororesin (B1a) is 15 g / 10 min or more, the moldability is excellent, and if it is 30 g / 10 min or less, the process stability is excellent.

The fluororesin (B1b) preferably has an MFR measured under conditions of a temperature of 230 ° C. and a load of 49 N of 1.0 to 14 g / 10 min, more preferably 1.0 to 10 g / 10 min, and 1.0 to 8.0 g / 10 min is more preferable. If the MFR of the fluororesin (B1b) is 1.0 g / 10 min or more, the moldability is excellent, and if it is 14 g / 10 min or less, the process stability is excellent.

  Examples of commercially available fluororesin (B1a) include “Kynar 720” (trade name, manufactured by Arkema Corp.), “Kynar 710” (trade name, manufactured by Arkema Corp.), “KFT # 850” (trade name). , Manufactured by Kureha Corporation). Examples of commercially available fluororesin (B1b) include “Kynar 740” (trade name, manufactured by Arkema Co., Ltd.), “KFT # 1000” (trade name, manufactured by Kureha Co., Ltd.), and “Solef 6010” (trade name). And Solvay Specialty Polymers Co., Ltd.).

The blending ratio of the fluororesin (B1a) / (B1b) is preferably 95/5 to 50/50% by mass, and 90/10 to 50/50% by mass with respect to the total 100% by mass of (B1a) and (B1b). % Is more preferable, and 90 / 10-60 / 40 mass% is still more preferable.
If the fluororesin (B1a) is 95% by mass or less, a film having excellent process stability, and if it is 50% by mass or more, a film in which defects such as die lines and blisters are suppressed on the film surface can be provided.

[Thermoplastic polymer (B2)]
The thermoplastic polymer (B2) is a thermoplastic polymer other than the fluororesin (B1), and is preferably a polymer obtained by polymerizing a monomer having a methacrylic acid alkyl ester as a main component. Examples of the thermoplastic polymer (B2) include thermoplastic polymers, polymer processing aids, and polymer matting agents described in International Publication No. 2014/192708. As the polymer matting agent, a polymer having a hydroxyl group described in JP-A No. 2003-342389 is preferable. The addition amount of the polymer matting agent can be appropriately set according to the required glossiness. Of course, if a high gloss level is required, a matting agent may not be included. When low glossiness is required, the addition amount of the matting agent is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, and still more preferably 10 to 15% by mass. The greater the amount of matting agent added, the lower the glossiness and the better matte appearance. Moreover, the smaller the addition amount of the matting agent, the more the softness of the fluorine-based resin composition (B) is not impaired, the better the stress whitening resistance, and the better the hot water whitening resistance.

[Additive C3]
The additive (C3) is a compound other than the fluororesin (B1) and the thermoplastic polymer (B2). For example, the stabilizer, lubricant, and processing aid described in International Publication No. 2014/192708. , Plasticizers, impact resistance improvers, foaming agents, fillers, colorants, and UV absorbers. However, it is preferable not to contain basic substances such as hindered amine light stabilizers because they may deteriorate the fluororesin.

  The surface appearance, optical characteristics, mechanical characteristics, etc. of the acrylic resin laminated film of the present invention can be said to be the same as those of the acrylic resin film (I) described above.

  As a method for producing the acrylic resin laminated film, a coextrusion method in which the resin layer (I) and the resin layer (II) are laminated while being melt-extruded at the same time is preferable because the production process can be reduced. As a method of laminating a plurality of molten resin layers, (1) a method of laminating a molten resin layer before passing through a die such as a feed block method, and (2) a method of laminating a molten resin layer in a die such as a multi-manifold method (3) A method of laminating a molten resin layer after passing through a die, such as a multi-slot method.

[Protective film, laminate with substrate]
The acrylic resin film (I) and the acrylic resin laminated film according to the present invention have excellent weather resistance and can be suitably used as a protective film for a substrate.

  A laminate (laminated molded product) is produced by laminating the acrylic resin film (I) and the acrylic resin laminated film of the present invention on the surface of a substrate such as various resin molded products, woodwork products, and metal molded products. Can do. A base material can be suitably selected according to the target laminated molded product. For example, in the case of a resin molded product, a thermoplastic resin such as a polyvinyl chloride resin, an olefin resin, an ABS resin, or a polycarbonate resin can be used.

  Examples of laminated molded products include exterior wall building materials such as window frames, entrance door frames, roofing materials, and siding materials that are attached to steel plates for the purpose of imparting design properties. When the base material has a two-dimensional shape and is a material that can be heat-sealed, the base material and the laminated film can be laminated by a method such as thermal lamination. What is necessary is just to laminate | stack by using an adhesive agent or carrying out the adhesive process of the single side | surface of a laminated | multilayer film with respect to the metal member etc. which are hard to heat-seal | fuse. Furthermore, you may give a bending process etc. after lamination | stacking, and the laminated | multilayer film of this invention can suppress the fall of design properties, such as whitening and a crack.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to these Examples. In the examples, “part” represents “part by mass”. Abbreviations in the examples are as follows.

MMA: methyl methacrylate BA: n-butyl acrylate AMA: allyl methacrylate HEMA: 2-hydroxyethyl methacrylate LPO: lauryl peroxide OTP: “Perex OT-P” (trade name) manufactured by Kao Corporation
nOM: n-octyl mercaptan CHP: NOF Corporation, “Park Mill H” (trade name)
tBH: NOF Corporation, “Perbutyl H” (trade name)
TV460: BASF, “Tinuvin460” (trade name)
TV1577: BASF, “Tinuvin1577” (trade name)
TV1600: BASF, “Tinuvin1600” (trade name)
TV234: BASF, “Tinuvin234” (product name)
C2020: manufactured by BASF, “Chimassorb2020” (trade name)
Irg1076: “Irganox1076” (trade name), manufactured by BASF
AO-60: “ADEKA STAB AO-60” (trade name), manufactured by ADEKA Corporation
T850: “KFT # 850” (trade name), manufactured by Kureha Corporation
T1000: “KFT # 1000” (trade name), manufactured by Kureha Corporation
VH: “Acripet VH001” (trade name), manufactured by Mitsubishi Chemical Corporation

The various physical properties in the examples were measured according to the following methods.
(1) Total light transmittance, haze, yellowness Total light transmittance is JIS K7361-1, haze is JIS K7136, yellowness is JIS.
The transmission method was evaluated according to K7373.

(2) Glossiness According to JIS Z8741, the 60 degree surface glossiness of the film was measured using a portable gloss meter (Konica Minolta Sensing Co., Ltd., trade name: GM-268). In the case of a laminated film, the resin layer (II) side was measured.

(3) Thickness of each layer of laminated film The laminated film is cut into an appropriate size, and using a reflection spectral film thickness meter FE3000 (trade name, manufactured by Otsuka Electronics Co., Ltd.), resin layers (I) and (II) The thickness of was measured.

(4) Tensile test The obtained film was cut into 150 mm × 15 mm with the film forming direction as the long side, and the distance between chucks was 100 mm using an autograph tensile tester (trade name, manufactured by Shimadzu Corp.) A tensile test was performed at a speed of 100 mm / min, and the elastic modulus, maximum point strength, and breaking elongation of the film were measured.

(5) Hot water test (visual)
The obtained film was cut into an appropriate size, immersed in 80 ° C. warm water for 48 hours, and the color after the test was visually evaluated according to the following criteria.
○: The film is not colored.
Δ: The film is slightly colored.
X: The film is colored.

(6) Hot water test (ΔYI)
The obtained film was cut into an appropriate size and immersed in warm water at 80 ° C. for 48 hours. For the films before and after the test, yellowness was measured by a reflection method in accordance with JIS K7373, and ΔYI was calculated by taking the difference. In the measurement, a white plate with YI = 0.1 was overlapped on the opposite side of the film measurement surface.

(7) Bending workability test A film is hot-pressed at 140 ° C. and laminated on a steel sheet decorative sheet obtained by laminating a black PVC layer having a thickness of 0.1 to 0.3 mm on a steel sheet having a thickness of 0.5 to 1.0 mm. A molded product was obtained. In the case of a laminated film, the resin layer (I) was laminated so as to be in contact with the black PVC layer. The temperature of the obtained laminated molded product was adjusted to −30 ° C., and then bent to 90 ° over 1 second with the steel plate side inward, and changes in the appearance of the laminated molded product were visually evaluated according to the following criteria.
○: The bent fulcrum part is not whitened.
Δ: The bent fulcrum portion is slightly whitened.
X: The bending fulcrum is whitened.

(8) Transmittance at 370 nm The transmittance at 370 nm was measured using an ultraviolet-visible spectrophotometer (product name: “V-630”, manufactured by JASCO Corporation).

(9) Gel content 50 ml of acetone was added to 0.5 g of the obtained resin composition (A), followed by stirring at 65 ° C. for 4 hours. Thereafter, the mixture was centrifuged at 14,000 rpm for 30 minutes at 4 ° C. After removing the supernatant, 50 ml of acetone was added again and centrifuged again under the same conditions. After removing the supernatant, the precipitated gel portion was vacuum-dried for 8 hours, the weight was measured, and the gel content was calculated by the following formula.
Gel content (%) = weight of gel part (g) /0.5×100

<Production Example 1: Production of core-shell rubber (A1-1)>
Into a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen introducing tube, 195 parts of deionized water was added, then 0.3 parts of MMA, 4.7 parts of BA and 0.08 parts of AMA, and OTP1 And a premixed mixture of 0.025 part of CHP and the temperature was raised to 60 ° C. After raising the temperature, a mixture of 5 parts of deionized water, 0.2 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA was added to initiate polymerization. After confirming the peak temperature, the reaction was continued for 15 minutes to complete the polymerization of the elastic polymer (A1a).

Subsequently, 3.0 parts of MMA, 47.0 parts of BA and 0.82 part of AMA, and 0.05 part of CHP were dropped into the polymerization vessel over 120 minutes. Thereafter, the reaction was continued for 60 minutes to complete the polymerization of the second elastic polymer (A2). Subsequently, 40.5 parts of MMA, BA
4.5 parts, 0.061 parts of tBH and 0.3 parts of nOM are dropped into the polymerization vessel over 120 minutes and the reaction is continued for 60 minutes to obtain a latex-like rubber-containing multistage polymer. It was.

The latex rubber-containing multistage polymer was dropped into 300 parts of hot water at 70 ° C. containing 3.8 parts of calcium acetate to coagulate the latex. Further, the temperature was raised to 95 ° C. and held for 5 minutes to solidify. The obtained coagulated product was separated and washed, and dried at 70 ° C. for 24 hours to obtain a powdery core-shell rubber (A1-1).

<Production Example 2: Production of core-shell rubber (A1-2)>
Core-shell rubber (A1-2) was obtained in the same manner as in Production Example 2 of International Publication No. 2014/192708.

<Production Example 3: Production of thermoplastic polymer (A2-1)>
The following monomer mixture (1) was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like. Next, after sufficiently replacing the inside of the container with nitrogen gas, the monomer mixture (1) in the reaction container was heated to 75 ° C. with stirring and reacted in a nitrogen gas stream for 3 hours. Thereafter, the temperature in the reaction vessel was raised to 90 ° C. and held for 45 minutes to complete the polymerization, followed by dehydration and drying to obtain a thermoplastic polymer (A2-1).

<Monomer mixture (1)>
MA: 1 part MMA: 79 parts HEMA: 20 parts nOM: 0.18 parts LPO: 1 part Tricalcium phosphate: 1.8 parts Deionized water: 250 parts

<Production Example 4: Production of thermoplastic polymer (A2-2)>
A thermoplastic polymer (A2-2) was obtained in the same manner as in Production Example 5 of International Publication No. 2014/192708.

<Production Example 5: Production of thermoplastic polymer (B2-1)>
A thermoplastic polymer (B2-1) was obtained in the same manner as in Production Example 1 except that the monomer mixture (1) was changed to the following monomer mixture (2).

<Monomer mixture (2)>
MA: 10 parts MMA: 60 parts HEMA: 30 parts nOM: 0.18 parts LPO: 1 part Tricalcium phosphate: 1.8 parts Deionized water: 250 parts

<Production Examples 6 and 7: Production of fluorine-based resin compositions (B-1) and (B-2)>
In Production Examples 6 and 7, raw materials such as fluororesin (B1) were mixed at a ratio as shown in Table 2 using a Henschel mixer, and a 35 mmφ screw type twin screw extruder (L / D = 26) Was used for melt-kneading and pelletizing under conditions of a cylinder temperature of 200 ° C. to 240 ° C. and a die temperature of 240 ° C. to obtain fluorine-based resin compositions (B-1) and (B-2).

<Example 1: Production of acrylic resin composition (A-1) and film>
In Example 1, an acrylic resin composition (A-1) was obtained in the same manner as in Production Example 6 except that the raw materials as shown in Table 1 were used. Subsequently, the acrylic resin composition (A-1) obtained was plasticized with a 30 mmφ extruder set at a cylinder temperature of 240 ° C., and a film having a thickness of 50 μm was formed using a single-layer T die set at 240 ° C. A film was formed. The evaluation results of the obtained film are shown in Table 3.

<Examples 2 and 3: Production of acrylic resin compositions (A-2) and (A-3) and films>
In Examples 2 and 3, acrylic resin compositions (A-2) and (A-3) and respective films were obtained in the same manner as in Example 1, except that the raw materials as shown in Table 1 were used. . The evaluation results of the obtained film are shown in Table 3.

<Comparative Examples 1-3: Production of Acrylic Resin Compositions (A-4) to (A-6) and Film>
In Comparative Examples 1-3, acrylic resin compositions (A-4) to (A-6) and respective films were obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used. . The evaluation results of the obtained film are shown in Table 3.

<Example 4: Creation of laminated film>
In Example 4, the acrylic resin composition (A-1) for the resin layer (I) obtained in Example 1 was dried at 80 ° C. all day and night, and T850 was used as the resin for the resin layer (II). It was. The acrylic resin composition (A-1) was plasticized with an extruder of 40 mmφ in which the cylinder temperature was set to 240 ° C. In addition, the resin composition T850 was plasticized with a 30 mmφ extruder provided with a 400 mesh screen mesh set at a cylinder temperature of 230 ° C. Then
Using a multi-manifold die for two types and two layers set at 240 ° C., a resin laminated film having a thickness of 50 μm was formed. The thicknesses of the resin layers (I) and (II) were 45 μm and 5 μm, respectively. Table 3 shows the evaluation results of the obtained laminated film.

<Examples 5 and 6: Creation of laminated film>
In Examples 5 and 6, each laminated film was obtained in the same manner as in Example 4 except that the resin for resin layer (II) as shown in Table 3 was used. Table 3 shows the evaluation results of the obtained laminated film.

  From the above examples and production examples, the following has become clear. The resin compositions and films obtained in Examples 1 to 6 had a transmittance at 370 nm of less than 1% and were excellent in ultraviolet shielding properties. Moreover, it was also excellent in hot water resistance and bending workability. On the other hand, the resin composition and film obtained in Comparative Example 1 had a transmittance at 370 nm of 1% or more and poor ultraviolet shielding properties. The resin composition and film obtained in Comparative Example 2 were inferior in warm water resistance. The resin composition and film obtained in Comparative Example 3 were inferior in bending workability.

  Although the present invention has been described with reference to the exemplary embodiments and examples, the present invention is not limited to the above exemplary embodiments and examples. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.

Claims (9)

The transmittance for light having a wavelength of 370 nm when the acrylic resin composition is formed into a film having a thickness of 50 μm is less than 1%,
Tensile modulus is 10 to 1,000 MPa,
The acrylic resin composition whose content of a triazine type ultraviolet absorber (C1) is 0.1-10 mass%. The acrylic resin composition according to claim 1, wherein the triazine-based ultraviolet absorber (C1) is represented by a structure of the following formula (1).
(1)
[In formula (1), G1 is hydrogen; C1-C18 alkyl; -OH, C2-C18 alkenyloxy, -C (O) OL1 and -OC (O) L2 (wherein L1 and L2 are independently C1-C18 alkyl substituted by 1, 2 or 3 groups selected from the group consisting of: C1-C18 alkyl; C3-C50 alkyl interrupted by oxygen; or C3-C50 interrupted by oxygen Hydroxyalkyl, G2, G3, G4 and G5 are independently hydrogen; C1-C18 alkyl; phenyl; or phenyl substituted by 1, 2 or 3 C1-C4 alkyl]   The acrylic resin composition of Claim 1 or 2 whose content of the said triazine type ultraviolet absorber (C1) is less than 2 mass%.   The acrylic resin composition as described in any one of Claims 1-3 whose content of a benzotriazole type ultraviolet absorber is less than 0.1 mass%.   The acrylic resin film which consists of an acrylic resin composition as described in any one of Claims 1-4.   A matte film comprising the acrylic resin film according to claim 5.   The acrylic resin laminated film which has resin layer (I) which consists of an acrylic resin composition as described in any one of Claims 1-4, and resin layer (II) which consists of a fluorine-type resin composition (B).   A protective film provided with the film of any one of Claims 5-7.   The protective film for decorative steel plates using the film of any one of Claims 5-7.