WO2015156323A1 - アクリル樹脂組成物、アクリル樹脂フィルム及び成形体 - Google Patents
アクリル樹脂組成物、アクリル樹脂フィルム及び成形体 Download PDFInfo
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- WO2015156323A1 WO2015156323A1 PCT/JP2015/060994 JP2015060994W WO2015156323A1 WO 2015156323 A1 WO2015156323 A1 WO 2015156323A1 JP 2015060994 W JP2015060994 W JP 2015060994W WO 2015156323 A1 WO2015156323 A1 WO 2015156323A1
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- Prior art keywords
- acrylic resin
- polymer
- resin composition
- monomer
- mass
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Definitions
- the present invention relates to a soft acrylic resin composition capable of forming a molded article such as an acrylic resin film having high weather resistance, heat resistance, transparency and stress whitening resistance.
- the decorative sheet laminated with this acrylic resin film when used in areas where the sunlight is strong at high temperatures such as the United States and Africa, has insufficient weather resistance, has a short usable period, and has insufficient heat resistance. And mechanical strength under high temperature is small. That is, even if an acrylic resin film is laminated on the surface of the polyvinyl chloride resin sheet, it is not suitable for use in areas where sunlight is strong at high temperatures.
- a method using a decorative sheet made of an acrylic resin instead of the polyvinyl chloride resin can be considered.
- acrylic resin is less flexible than polyvinyl chloride resin. Therefore, for example, when the decorative sheet is bonded to a base material such as a steel plate, and the base material is bent at room temperature to form various members such as a window frame, the decorative sheet may be cracked at the bent portion. . And the base material exposed by the crack has a problem that it is exposed to sunlight and corroded.
- the kind and ratio of the monomers used in the hard polymer in the multistage polymer as described above are adjusted, and the glass transition temperature (Tg) of the acrylic resin.
- Tg glass transition temperature
- Patent Document 3 an acrylic resin composition having both heat resistance and flexibility has been proposed.
- the molded body obtained from this acrylic resin composition has a haze in appearance, and also has a problem of stress whitening at room temperature, and this acrylic resin composition is suitable for members that require high design properties. It has been difficult to apply or apply to members that require bending at room temperature.
- An object of the present invention is to provide an acrylic resin composition having high weather resistance, flexibility, heat resistance, transparency, and stress whitening resistance. Especially suitable for use in a wide area, including areas where sunlight is strong at high temperatures, and problems such as whitening and cracking do not occur even when bonded to a substrate at room temperature, and high design is achieved with sufficient transparency.
- An object of the present invention is to provide an acrylic resin composition suitable as a material for producing a molded body such as a film that can be applied.
- the total light transmittance value of the body is 90% or more
- the test piece 1 having a length of 80 mm and a width of 15 mm made of the molded body, or the acrylic resin composition is formed by a T-die method.
- Test piece 2 having a thickness of 0.05 to 0.1 mm, a length of 80 mm, and a width of 15 mm;
- the initial chuck distance is 25 mm
- the tensile speed is 500 mm / min at a temperature of 23 ° C.
- the whiteness difference ⁇ W before and after stretching is 10 or less at the end chuck distance of 35 mm. is there,
- the acrylic resin composition [2] The acrylic resin composition according to [1], wherein the molded body has a haze value of 2% or less.
- a test piece 3 having a thickness of 0.05 to 0.1 mm, a length of 150 mm, and a width of 15 mm obtained by forming a film of the acrylic resin composition by the T-die method has the following conditions (3) and The acrylic resin composition according to [1] or [2], which satisfies (4); (3): The elongation at break when stretched at a temperature of 0 ° C. and a tensile speed of 50 mm / min is 20 to 300%, (4): The elongation at break when stretched at a temperature of 23 ° C. and a tensile speed of 50 mm / min is 100 to 500%.
- a rubber-containing multistage polymer (I) One or more monomers selected from the group consisting of an alkyl acrylate (a1) having an alkyl group having 1 to 8 carbon atoms and an alkyl methacrylate (a2) having an alkyl group having 1 to 4 carbon atoms;
- An elastic polymer (A) obtained by polymerizing the monomer (a) containing the monomer (a4), and
- a hard polymer (B) obtained by polymerizing a monomer (b) containing an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms in the presence of the elastic polymer (A),
- the elastic polymer (A) is a graft polymer produced using a graft crossing agent, and the content of the graft crossing agent unit in 100% by mass of the elastic polymer (A) is 1.3% by mass. % Or more of the acrylic resin composition according to any one of [1] to [5].
- Acrylic resin composition [9] Any of [1] to [8] above, wherein the total content of the monomer (a1) unit and the monomer (a2) unit in the elastic polymer (A) is 80% by mass or more.
- an acrylic resin composition having high weather resistance, flexibility, heat resistance, transparency, and stress whitening resistance is provided. If this acrylic resin composition is used, it is a molded article suitable for use in a wide area including areas where sunlight is strong at high temperatures. It is possible to produce a molded body such as a highly designable film that does not cause this problem.
- the acrylic resin composition of the present invention contains a rubber-containing multistage polymer (I) containing 30% by mass or more of an elastic polymer (A), (1) A 1 mm-thick molded product produced by heating and melting the powdery acrylic resin composition, pressurizing at a temperature of 200 ° C. and a pressure of 5 MPa for 5 minutes, and then cooling for 5 minutes while applying a pressure of 2 MPa. (2) Obtained by forming the test piece 1 having a length of 80 mm and a width of 15 mm made of the molded body, or the acrylic resin composition by the T-die method.
- a test piece 2 having a thickness of 0.05 to 0.1 mm, a length of 80 mm, and a width of 15 mm,
- the initial chuck distance is 25 mm
- the tensile speed is 500 mm / min at a temperature of 23 ° C.
- the whiteness difference ⁇ W before and after stretching is 10 or less at the end chuck distance of 35 mm. is there.
- the first characteristic of the acrylic resin composition of the present invention is that a sheet-like molded product having a thickness of 1 mm formed therefrom has a total light transmittance of 90% or more.
- the total light transmittance is measured according to ISO13468.
- As a compact suitable for measuring the total light transmittance for example, it is sandwiched between SUS plates and heated and melted at a temperature of 200 ° C. and a pressure of 0 MPa for 10 minutes, and then pressurized at a temperature of 200 ° C. and a pressure of 5 MPa for 5 minutes, and then a pressure of 2 MPa. 1 mm thick molded body produced by cooling for 5 minutes while applying
- the “T-die method” means a method for producing a film using a T-die.
- L / D 40 mm diameter non-vent screw type extruder
- the degree of whiteness of the acrylic resin composition of the present invention is measured by stretching the test piece obtained as described above by 10 mm from a chuck distance of 25 mm to 35 mm at a temperature of 23 ° C. under a pulling speed of 500 mm / min. can do.
- the difference in W value before and after the tensile test is 1 or less, preferably 0.8 or less.
- the W value is a value measured using a C / 2 ° light source according to the geometric condition a of JIS Z 8722.
- the W value is a value obtained by quantifying the whiteness, and is an index value for stress whitening resistance.
- the molded body obtained from the acrylic resin composition of the present invention preferably has a haze value of 2% or less.
- a molded product having a thickness of 1 mm prepared in the same manner as in the case of [total light transmittance] is used with a haze measuring instrument, for example, a haze meter (HR-100, manufactured by Murakami Color Research Laboratory).
- a haze measuring instrument for example, a haze meter (HR-100, manufactured by Murakami Color Research Laboratory).
- HR-100 haze meter
- the acrylic resin composition of the present invention has a film obtained by molding the acrylic resin composition in a thickness of 0.05 to 0.1 mm and a width of 15 mm in accordance with ISO 527-3, and (3): The elongation at break when stretched at a temperature of 0 ° C. and a tensile speed of 50 mm / min is 20 to 300%, and (4): the elongation at break when stretched at a temperature of 23 ° C. and a tensile speed of 50 mm / min. The degree is preferably 100 to 500%. When the elongation at break at 20 ° C.
- the elongation at break is 20% or more, for example, when the film is stretched or bent in a cold district or a low temperature environment, the film is not easily broken, so that workability is improved.
- the handleability becomes good, for example, when an excess part of the processed film is cut off.
- the breaking elongation at 0 ° C. is more preferably 30 to 300%, still more preferably 40 to 300%.
- the breaking elongation at 23 ° C. is 100% or more, the film does not break when the film is stretched or bent, so that the workability is good.
- the elongation at break is 500% or less, the handleability becomes good when, for example, cutting off an excess portion of the processed film.
- the elongation at break at 23 ° C. is more preferably 120 to 500%, still more preferably 130 to 500%.
- the tensile direction can be two directions: MD direction (machine Direction, longitudinal direction) and TD direction (Traverse Direction transverse direction).
- MD direction machine Direction, longitudinal direction
- TD direction Traverse Direction transverse direction
- breaking elongation is MD Both the direction and the TD direction are satisfied (if any is out of the above range, it is out of the scope of the present invention).
- a test piece having a thickness of 4 mm molded therefrom exhibits a bending elastic modulus of 400 MPa or more. More specifically, in accordance with ISO178, for a test piece having a thickness of 4 mm, a length of 80 mm, and a width of 10 mm, a load is applied to the center of the test piece at a temperature of 23 ° C., a distance between fulcrums of 64 mm, and a test speed of 2 mm / min. It is preferable that the value of the flexural modulus calculated from the bending stress when the deflection amount is 0.088 mm and 0.44 mm is 400 MPa or more.
- the flexural modulus is 400 MPa or more, an appropriate strength can be imparted to the resin, and a stable performance can be exhibited during production or construction.
- the crosslinkable monomer (a4) contained in 100% by mass of the elastic polymer (A) of the rubber-containing multistage polymer (I) (described later) It is effective that the amount of the graft-crossing agent unit is 1.3% by mass or more.
- the acrylic resin composition of the present invention preferably has an MFR value of 1 g / 10 min or more measured under conditions of a temperature of 230 ° C. and a load of 5.0 kg in accordance with ASTM D-1238.
- MFR is an index value of molding processability, and if it is 1 g / 10 min or more, it is preferable because a resin stay hardly occurs during the molding process.
- the acrylic resin composition of the present invention contains a rubber-containing multistage polymer (I) containing 30% by mass or more of the elastic polymer (A).
- the rubber-containing multistage polymer (I) is one or more selected from the group consisting of an alkyl acrylate (a1) having an alkyl group having 1 to 8 carbon atoms and an alkyl methacrylate (a2) having an alkyl group having 1 to 4 carbon atoms.
- the elastic polymer (A) obtained by polymerizing the monomer (a) containing the monomer (a) and the crosslinkable monomer (a4), and the elastic polymer (A).
- a rubber-containing multistage polymer including a hard polymer (B) obtained by polymerizing a monomer (b) containing an alkyl methacrylate having an alkyl group of 1 to 4 is preferable.
- Alkyl acrylate (a1) having an alkyl group of 1 to 8 carbon atoms (hereinafter referred to as “monomer (a1)” or “alkyl acrylate (a1)”) used as a raw material for the elastic polymer (A). ) May be linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. You may use these individually by 1 type or in combination of 2 or more types.
- an alkyl acrylate having a low glass transition temperature (Tg) is preferable, and n-butyl acrylate is more preferable. If Tg is low, the elastic polymer (A) has good impact resistance and can be easily molded.
- Alkyl methacrylate (a2) having an alkyl group having 1 to 4 carbon atoms (hereinafter referred to as “monomer (a2)” or “alkyl methacrylate (a2)”) used as a raw material for the elastic polymer (A). ) May be linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. You may use these individually by 1 type or in combination of 2 or more types.
- alkyl acrylate (a1) and alkyl methacrylate (a2) may be used, or a combination of both may be used.
- the proportion of the alkyl acrylate (a1) is preferably 50% by mass or more in 100% by mass of the monomer used as a raw material for the elastic polymer (A).
- the ratio of the monomer (a1) unit / monomer (a2) unit in the elastic polymer (A) was 100, where the total mass of the monomer (a1) unit and the monomer (a2) unit was 100.
- the mass ratio of monomer (a1) unit: monomer (a2) unit is preferably 50:50 to 100: 0.
- a monomer (a3) having a double bond other than the alkyl acrylate (a1) and the alkyl methacrylate (a2) (hereinafter referred to as “monomer ( a3) "may also be used.
- Examples of the monomer (a3) include acrylate monomers such as higher alkyl acrylate, lower alkoxy acrylate, and cyanoethyl acrylate having an alkyl group having 9 or more carbon atoms, acrylamide, acrylic acid, methacrylic acid, styrene, and alkyl-substituted styrene. , Acrylonitrile, and methacrylonitrile.
- the crosslinkable monomer (a4) forms a crosslink with the alkyl acrylate (a1) and / or the alkyl methacrylate (a2) to give rubber elasticity to the polymer, and crosslinks with the hard polymer (B). It is a component to be formed.
- a graft crossing agent having a function of causing a graft crossover reaction together with a crosslinking reaction is preferable. Examples of such functions include allyl, methallyl or crotyl esters of copolymerizable ⁇ , ⁇ -unsaturated carboxylic acid or dicarboxylic acid. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid.
- allyl methacrylate has an excellent effect.
- triallyl cyanurate and triallyl isocyanurate are also effective.
- Graft-crossing agents are chemically bonded, mainly because the conjugated unsaturated bonds of their esters react much faster than allyl, methallyl or crotyl groups. Meanwhile, the substantial majority of allyl, methallyl or crotyl groups in the graft crossing agent remain unreacted and react during polymerization of the next layer polymer to give graft bonds between 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 graft crossover.
- 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 can also be used.
- various monomers can be selected as the crosslinkable monomer (a4).
- a graft crossing agent such as allyl methacrylate.
- the monomer (a) including the monomer (a1), monomer (a2), monomer (a3) and crosslinkable monomer (a4), alkyl acrylate (a1) and
- the total amount of alkyl methacrylate (a2) is preferably 80 to 100% by mass, and the amount of monomer (a3) is preferably 0 to 20% by mass.
- the amount of the graft crossing agent in the crosslinkable monomer (a4) is preferably 3.0% by mass or less in 100% by mass of the monomer (a) from the viewpoint of imparting sufficient flexibility to the acrylic resin. 1.3 mass% or less is more preferable. If the amount of the graft crossing agent is 3.0% by mass or less, the cross-linking between the elastic polymer (A) and the hard polymer (B) is not strong, and the acrylic resin has sufficient softness. .
- a single unit containing the above monomer (a1), monomer (a2), monomer (a3) and crosslinkable monomer (a4) In 100% by mass of monomer (a), the total amount of alkyl acrylate (a1) and alkyl methacrylate (a2) is 80 to 98.7% by mass, and the amount of monomer (a3) is 0 to 18.7% by mass. preferable.
- the amount of the grafting agent in the grafting agent in the crosslinkable monomer (a4) is preferably 1.3% by mass or more, more preferably 1.6% by mass or more in 100% by mass of the monomer (a). .
- an upper limit is not specifically limited, For example, it is about 6.0 mass% or less.
- the amount of the graft crossing agent is 1.3% by mass or more, the crosslinking between the elastic polymer (A) and the hard polymer (B) becomes stable, and sufficient transparency is exhibited. Moreover, rubber elasticity can be improved more and the impact resistance of the molded object obtained increases.
- Monomer (a) 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, the particle diameter of the finally obtained rubber-containing multistage polymer (I) can be easily controlled.
- the elastic polymer (A) can be obtained by a polymerization method such as emulsion polymerization or suspension polymerization.
- a polymerization method such as emulsion polymerization or suspension polymerization.
- emulsion polymerization it is preferable to use an emulsifier, a radical polymerization initiator, and a chain transfer agent.
- an anionic, cationic or nonionic surfactant can be used as the emulsifier.
- An anionic surfactant is particularly preferable.
- Specific examples of the anionic surfactant include the following. Rosin acid soap, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate, sulfate esters such as sodium lauryl sulfate, dioctyl sodium sulfosuccinate, dodecylbenzene Sulfonates such as sodium sulfonate, sodium alkyldiphenyl ether disulfonate, phosphate esters such as polyoxyethylene alkylphenyl ether sodium phosphate, and the like.
- Examples of methods for preparing an emulsion include (1) a method in which a monomer mixture is charged into water and then a surfactant is added, and (2) a monomer mixture is charged after the surfactant is charged in water. And (3) a method in which water is added after the surfactant is charged into the monomer mixture.
- the methods (1) and (2) are preferred.
- radical polymerization initiator examples include the following. Persulfates such as potassium persulfate and sodium persulfate; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide and benzoyl peroxide; azo compounds such as azobisisobutyronitrile; these persulfuric acids Redox initiators in which a salt or organic peroxide and a reducing agent are combined. Among them, a redox initiator is preferable, and a sulfoxylate initiator in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate, and hydroperoxide are combined is more preferable.
- the radical polymerization initiator can be added to either one or both of the aqueous phase and the monomer phase.
- chain transfer agent examples 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 (B).
- the polymerization temperature varies depending on the type and amount of the polymerization initiator, but is preferably 40 to 120 ° C, more preferably 60 to 95 ° C.
- the core part having a Tg exceeding 0 ° C. may be polymerized prior to the polymerization of the elastic polymer (A).
- the core is preferably 0 to 10% by mass in the rubber-containing multistage polymer (I).
- the core consists of 10 to 50% by weight of monomer (a1), 20 to 70% by weight of monomer (a2), 0 to 10% by weight of monomer (a3), and 0. 10% by weight of crosslinkable monomer (a4). Those obtained by polymerizing 100% by mass of the monomer (a) consisting of 1 to 10% by mass are preferred.
- the Tg of the elastic polymer (A) is preferably 0 ° C. or lower, more preferably ⁇ 30 ° C. or lower.
- Tg is 0 ° C. or lower, the obtained molded article has preferable impact resistance.
- This Tg is a value measured as follows using a dynamic viscoelasticity measuring apparatus. First, the acrylic resin composition is melted and formed into a sheet having a thickness of 1 mm and a width of 6 mm, and then a test piece having dimensions of a thickness of 1 mm, a width of 6 mm, and a length of 65 mm is obtained.
- the distance between the initial chucks is 2 cm
- the measurement frequency is 0.1 Hz
- the measurement temperature range is -90 to 150 ° C.
- the heating rate is 2 ° C./min
- the nitrogen stream is 200 mL.
- Measure the storage elastic modulus (E ′) and loss elastic modulus (E ′′) of the test piece in the tensile mode under the conditions of / min and according to the formula “tan ⁇ E ′′ / E ′”.
- the value of tan ⁇ (loss tangent) at each temperature is calculated.
- two or more peaks appear. Among these, the temperature corresponding to the peak appearing on the lowest temperature side is defined as Tg of the elastic polymer (A).
- the rubber-containing multistage polymer (I) polymerizes the monomer (b) containing an alkyl methacrylate (b1) having an alkyl group having 1 to 4 carbon atoms in the presence of the elastic polymer (A) described above. It is preferable to obtain it.
- the monomer (b) can form a hard polymer (B) by polymerization.
- alkyl methacrylate (b1) are the same as the specific examples of the alkyl methacrylate (a2) described above. You may use them individually by 1 type or in combination of 2 or more types.
- a monomer (b2) having a double bond other than the alkyl methacrylate (b1) (hereinafter sometimes referred to as “monomer (b2)”) may be further used.
- Specific examples of the monomer (b2) include the same examples as the specific examples of the alkyl acrylate (a1) and the monomer (a3) described above. You may use them individually by 1 type or in combination of 2 or more types.
- the amount of alkyl methacrylate (b1) is preferably 70% by mass or more, and more preferably 85% by mass or more. Thereby, Tg of the hard polymer (B) formed by polymerizing only the monomer (b) can be appropriately increased.
- Monomer (b) may be polymerized in two or more stages. In that case, monomer mixtures having different compositions may be polymerized.
- the polymerization reaction of the monomer (b) is preferably continued after the polymerization reaction of the elastic polymer (A) is completed, using the obtained polymerization liquid as it is, and adding the monomer (b).
- Specific examples of the emulsifier, radical polymerization initiator, and chain transfer agent in this polymerization are the same as the specific examples in the polymerization of the elastic polymer (A) described above.
- the amount of the chain transfer agent is preferably 0.01 to 1.5 parts by weight, more preferably 0.05 to 1.0 parts by weight with respect to 100 parts by weight as the total of the monomers (a) and (b). 0.1 to 0.5 parts by mass is more preferable. When this amount is 0.01 parts by mass or more, the molded article has high flexibility, and when it is 1.5 parts by mass or less, the mechanical strength of the molded article tends to increase.
- Tg of a hard polymer (B) is 85 degreeC or more, More preferably, it is 90 degreeC or more.
- Tg of the hard polymer (B) is a temperature corresponding to a peak appearing on the highest temperature side (80 ° C. or higher) in the dynamic viscoelasticity measurement of the rubber-containing multistage polymer (I).
- the intermediate polymer (C) includes an alkyl acrylate (c1) having an alkyl group having 1 to 8 carbon atoms (hereinafter sometimes referred to as “monomer (c1)”) and an alkyl having 1 to 4 carbon atoms.
- An alkyl methacrylate (c2) having a group hereinafter sometimes referred to as “monomer (c2)”
- another monomer (c3) having a copolymerizable double bond used as necessary
- the crosslinkable monomer (c4) used as necessary is preferably used as a constituent component.
- monomer (c1), monomer (c2), monomer (c3), and crosslinkable monomer (c4) are the simple examples of the elastic polymer (A) described above.
- monomer (a1), the monomer (a2), the monomer (a3), and the crosslinkable monomer (a4) are the same.
- the amount of monomer (c1) is 10 to 10%. 90% by mass
- the amount of the monomer (c2) is 10 to 90% by mass
- the amount of the monomer (c3) is 0 to 20% by mass
- the amount of the crosslinkable monomer (c4) is 0 to 10% by mass. It is preferable that
- the proportion of the intermediate polymer (C) in 100% by mass of the rubber-containing multistage polymer (I) is preferably 0 to 35% by mass, and more preferably 5 to 15% by mass.
- the ratio of the elastic polymer (A) / intermediate polymer (C) / hard polymer (B) is 50 to 60% by mass / 5 to 15% by mass / It is preferably 25 to 45% by mass.
- the ratio of the elastic polymer (A) / hard polymer (B) is preferably 50 to 70% by mass / 30 to 50% by mass.
- the ratio of the elastic polymer (A) in 100% by mass of the rubber-containing multistage polymer (I) is 30% by mass or more. If this ratio is 30% by mass or more, the mechanical strength and flexibility of the obtained molded body are further improved, and cracks can be suppressed. In particular, when the molded body is a film, breakage during molding can be suppressed. In addition, when laminated on the surface of various three-dimensional shaped resin molded products, woodwork products or metal molded products directly or after being laminated on various resin sheets and heated above the softening temperature, breakage, cracks, whitening are suppressed, and the design A molded article with high properties can be obtained. Such a molded body is also suitable for processing at room temperature.
- the proportion of the hard polymer (B) is preferably 70% by mass or less, more preferably 20 to 70% by mass.
- the emulsion polymerization method it is preferable to recover the rubber-containing multistage polymer (I) as a powder from the latex after completion of the polymerization reaction.
- a method for recovering as a powder for example, the latex is contacted with a coagulant to coagulate or salt out, solid-liquid separate, washed with water about 1 to 100 times the mass of the polymer, and then subjected to 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.
- 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.
- the coagulant examples include organic salts such as sodium acetate, calcium acetate, potassium formate and calcium formate, and inorganic salts such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride and sodium sulfate.
- 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.
- calcium salts such as calcium acetate and calcium chloride are preferable.
- 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.
- a coagulant may be used alone or in combination of two or more. The coagulant is usually used as an aqueous solution.
- the concentration of the aqueous solution of the coagulant 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 the coagulant, preferably calcium acetate, is low in the amount of the coagulant remaining in the collected powder, and particularly from the point of hardly reducing the performance of the molded product such as hot water whitening resistance and colorability. 20 mass% or less is preferable and 15 mass% or less is more preferable. In addition, 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.
- the amount of the aqueous solution of the coagulant is preferably 10 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the latex.
- the temperature in the solidification step is preferably 30 ° C. or higher and 100 ° C. or lower.
- the mass average molecular weight of the acetone-soluble component of the rubber-containing multistage polymer (I) is preferably 40000 or more, and more preferably 60000 or more. If the mass average molecular weight is 40000 or more, the mechanical strength of the obtained molded body is improved and cracking can be suppressed. In particular, when the molded body is a film, breakage during molding can be suppressed. Furthermore, when the film is laminated alone or on various resin sheets and heated above the softening temperature and laminated on the surface of various three-dimensional shaped resin molded products, woodwork products, or metal molded products, breakage and cracking can be suppressed. The molded body has high mechanical strength and is easy to handle.
- the molded body when the molded body is bonded to a base material such as a steel plate and then bent into a window frame or the like at room temperature, breakage and cracking can be suppressed, and the base material is not exposed and exposed to sunlight or the like. It will not corrode. Moreover, if the said mass mean molecular weight is 60000 or more, the stress whitening resistance of the molded object obtained will express. Further, the molded body has high mechanical strength and is easy to handle.
- the said mass mean molecular weight is a value measured by gel permeation chromatography (GPC) about the acetone soluble part in rubber-containing multistage polymer (I). Specifically, it is measured by the following methods [1] to [3]. [1] 1 g of rubber-containing multistage polymer (I) is dissolved in 50 g of acetone and refluxed at 70 ° C. for 4 hours to obtain an acetone-soluble component. [2] The obtained extract is centrifuged at 14000 rpm at 4 ° C. for 30 minutes using CRG SERIES (manufactured by Hitachi, Ltd.). [3] Acetone-insoluble matter was removed by decantation, and the acetone-soluble matter obtained by drying at 50 ° C.
- GPC gel permeation chromatography
- the mass average molecular weight of the acetone-soluble component of the rubber-containing multistage polymer (I) can be adjusted by appropriately changing the amount of the chain transfer agent during the polymerization.
- a master batch is prepared by mixing a part of the total amount of the rubber-containing multistage polymer (I) and, if necessary, a compounding agent. Furthermore, it can also be obtained by multi-stage blending mixed with the remainder of the rubber-containing multistage polymer (I).
- a compounding agent is mixed to obtain a single screw extruder or a twin screw extruder.
- the acrylic resin composition of the present invention may contain a rubber-containing multistage polymer (I) and further a thermoplastic polymer (II).
- the thermoplastic polymer (II) preferably used in the present invention has a reduced viscosity comprising 50 to 100% by mass of methyl methacrylate units and 0 to 50% by mass of one or more vinyl monomer units copolymerizable therewith. Is a polymer having 0.2 to 2 dL / g.
- the thermoplastic polymer (II) the moldability of the acrylic resin composition can be improved.
- the melt tension of the acrylic resin composition is increased. Therefore, in the case of melt extrusion into a film, it is possible to prevent the discharge amount from decreasing and the productivity from deteriorating.
- the thickness accuracy of a molded body such as a film can be improved.
- Examples of the vinyl monomer copolymerizable with methyl methacrylate used in the thermoplastic polymer (II) include aromatic vinyl monomers, vinyl cyanide monomers, alkyl methacrylates other than methyl methacrylate, and alkyl acrylates. It is done.
- Specific examples of the aromatic vinyl monomer include styrene, ⁇ -substituted styrene, nucleus-substituted styrene and derivatives thereof (for example, ⁇ -methylstyrene, chlorostyrene, vinyltoluene).
- Specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.
- alkyl methacrylate other than methyl methacrylate examples include ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
- alkyl methacrylate examples include butyl methacrylate.
- Specific examples of the alkyl acrylate are the same as the specific examples of the alkyl acrylate (a1) used for the elastic polymer (A) described above.
- the thermoplastic polymer (II) can be obtained by a polymerization method such as emulsion polymerization or suspension polymerization. Among these, emulsion polymerization is preferable because the polymer can be obtained in a powder or granular form. In the case of emulsion polymerization, it is preferable to use an emulsifier, a radical polymerization initiator, and a chain transfer agent. Specific examples thereof are the same as the specific examples of the emulsifier, the radical polymerization initiator and the chain transfer agent used in the rubber-containing multistage polymer (I) described above.
- the polymerization temperature varies depending on the type and amount of the polymerization initiator, but is preferably 40 to 80 ° C.
- thermoplastic polymer (II) as a powder from the latex after completion of the emulsion polymerization reaction is the same as the method for recovering the rubber-containing multistage polymer (I) described above as a powder.
- the reduced viscosity of 0.1 g of thermoplastic polymer (II) dissolved in 100 mL of chloroform and measured at 25 ° C. is 0.2 to 2 dL / g. If this reduced viscosity is 0.2 dL / g or more, the melt tension of the acrylic resin composition is sufficient, and the effect of improving the moldability at the time of melt extrusion, the discharge amount accuracy at the time of melt extrusion, and the thickness accuracy of the film is manifested. To do. Moreover, if it is 2 dL / g or less, compatibility with rubber-containing multistage polymer (I) will become enough, and the melt tension of the moldability of an acrylic resin composition can be improved.
- the blending amount of the thermoplastic polymer (II) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber-containing multistage polymer (I). If the blending amount is 0.1 parts by mass or more, the melt tension of the acrylic resin composition can be sufficiently increased, and the effect of improving the moldability at the time of melt extrusion, the discharge amount accuracy, and the film thickness accuracy is sufficient. To express. Moreover, if it is 10 mass parts or less, the melt tension of an acrylic resin composition will not become high too much, and the deterioration of the surface appearance of a molded object can be prevented.
- the rubber-containing multistage polymer (I) and the thermoplastic polymer (II) are separately collected as powders, and they are extruded and kneaded.
- the rubber-containing multistage polymer (I) and the thermoplastic polymer (II) are obtained by emulsion polymerization by roll kneading or other methods, the polymerization reaction of the rubber-containing multistage polymer (I) is completed.
- the later latex and the latex after completion of the polymerization reaction of the thermoplastic polymer (II) are mixed and then recovered as a powder.
- the acrylic resin composition of the present invention may contain various compounding agents as necessary.
- compounding agents include stabilizers, lubricants, plasticizers, impact resistance aids, fillers, antibacterial agents, antifungal agents, foaming agents, mold release agents, antistatic agents, colorants, matting agents, and UV absorption agents.
- Agents thermoplastic polymers.
- a compounding agent can be added to latex containing a polymer, and a mixture of the compounding agent and the polymer can be recovered as a powder. Moreover, you may mix a compounding agent with the powder collect
- recovered from latex to the kneading machine accompanying a molding machine.
- the kneader associated with the molding machine include a single screw extruder and a twin screw extruder.
- the acrylic resin composition of the present invention comprises 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole and / or 2- [4,6-bis (biphenyl).
- -4-yl) -1,3,5-triazin-2-yl] -5-[(2-ethylhexyl) oxy] phenol may further be included. These may be used alone or in combination. Moreover, you may use together with another additive.
- bleed out refers to a phenomenon in which, when a molded body is heated while being humidified, additives and the like float on the surface of the molded body and the molded body becomes cloudy. For example, if it is humidified and heated at 80 ° C. and 90 RH% for 10 hours and it can be visually confirmed that the surface of the molded body is not white and cloudy, it can be determined that the bleed-out resistance is excellent.
- 2- [2-Hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole used in the present invention is commercially available as Tinuvin 234 and Tinuvin 900 from BASF Japan Ltd.
- 2- [4,6-bis (biphenyl-4-yl) -1,3,5-triazin-2-yl] -5-[(2-ethylhexyl) oxy] phenol is a product of BASF Japan Ltd. It is industrially available as Tinuvin 1600 (all are trade names).
- the acrylic resin composition of the present invention recovers, for example, the rubber-containing multistage polymer (I) as a powder and 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl]- Mixers such as 2H-benzotriazole and / or 2- [4,6-bis (biphenyl-4-yl) -1,3,5-triazin-2-yl] -5-[(2-ethylhexyl) oxy] phenol And then melt-mixed by a method such as extrusion kneading or roll kneading.
- 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl]- Mixers such as 2H-benzotriazole and / or 2- [4,6-bis (biphenyl-4-yl) -1,3,5-triazin-2-yl] -5-[(2-ethylhexyl) oxy]
- thermoplastic polymer (II) recovered as a powder is mixed with the above-mentioned rubber-containing multistage polymer (I) with a mixer, etc., and melt mixed by a method such as extrusion kneading or roll kneading. Obtainable.
- the rubber-containing multistage polymer (I) and the thermoplastic polymer (II) are obtained by emulsion polymerization, respectively, the latex and the thermoplastic polymer (II) after completion of the polymerization reaction of the rubber-containing multistage polymer (I)
- the acrylic resin composition of the present invention can also be obtained by mixing with the latex after completion of the polymerization reaction and then collecting the powder containing both polymers.
- the acrylic resin composition of the present invention is, for example, firstly a part of the total amount of the rubber-containing multistage polymer (I), 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl]. -2H-benzotriazole and / or 2- [4,6-bis (biphenyl-4-yl) -1,3,5-triazin-2-yl] -5-[(2-ethylhexyl) oxy] phenol, heat
- a master batch can be prepared by mixing the plastic polymer (II) and, if necessary, a compounding agent, and this master batch can be obtained by multi-stage compounding further mixed with the remainder of the rubber-containing multi-stage polymer (I). it can.
- the molded body obtained by molding the acrylic resin composition of the present invention may have any shape such as a film, a sheet, and a three-dimensional structure.
- a film-like molded body is particularly preferable.
- uses of such molded articles include, for example, agricultural vinyl houses, marking films, posters, wallpaper, foam sheets, outdoor PVC leather, PVC steel roofing materials such as roofing materials and siding materials, automobile interior and exterior, and furniture. Coating substitutes such as elevator interiors, rain gutters, flooring, corrugated sheets, decorative columns, lighting, and coating materials for water-related members such as bathrooms and kitchens.
- the “film-like molded body” includes a sheet.
- the acrylic resin composition of the present invention is subjected to, for example, melt extrusion molding such as solution casting method, T-die method, inflation method, calendar molding, injection molding, vacuum molding, blow molding, mold molding, compression molding, etc.
- melt extrusion molding such as solution casting method, T-die method, inflation method, calendar molding, injection molding, vacuum molding, blow molding, mold molding, compression molding, etc.
- the melting temperature at the time of molding is preferably 100 to 280 ° C.
- the acrylic resin composition of the present invention is formed into a film, it is preferable to form the film by calendering or the T-die method.
- the thickness of the film is preferably 0.01 to 0.5 mm, more preferably 0.015 to 0.2 mm, and still more preferably 0.04 to 0.2 mm. When the thickness of the film is within these ranges, the film has an appropriate rigidity, and good laminating properties and secondary workability.
- the acrylic resin film of the present invention may be used as it is for various applications, or may be used by being laminated on a substrate. If this transparent acrylic resin film is laminated on a base material, it becomes an alternative to clear coating, and the color tone of the base material can be utilized. Thus, in applications that make use of the color tone of the substrate, acrylic resin films are superior in terms of transparency, depth, and luxury compared to polyvinyl chloride films and polyester films.
- a base material the molded article and woodwork products which consist of metals, such as various resin or a steel plate, are mentioned, for example.
- the resin constituting the substrate is preferably a thermoplastic resin that can be melt-bonded to the acrylic resin film.
- thermoplastic resin examples include acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or the main component thereof. Resin. Among these, ABS resin, AS resin, polycarbonate resin, vinyl chloride resin or a resin mainly composed of these resins is preferable from the viewpoint of adhesiveness. In the case of a substrate made of a resin that is difficult to melt and bond, such as a polyolefin resin, an acrylic resin film may be laminated after appropriately providing an adhesive layer.
- the base material and the acrylic resin film can be laminated by a method such as thermal lamination.
- a method such as thermal lamination.
- an adhesive may be used, or one side of the acrylic resin film may be adhesively processed and laminated.
- a bending process etc. may be given after lamination
- the base material has a three-dimensional shape, an insert molding method in which an acrylic resin film processed into a predetermined shape in advance is inserted into an injection mold, and an in-mold molding method in which injection molding is performed after vacuum molding in the mold.
- a base material and an acrylic resin film can be laminated
- the in-mold molding method is to form an acrylic resin film into a three-dimensional shape by vacuum molding, and then to inject the resin that is the raw material of the base material into the molded body by injection molding.
- the laminated body which has a resin film can be obtained easily, and is preferable.
- the acrylic resin film can be molded and injection molded in one step, which is preferable from the viewpoint of excellent workability and economy.
- an ultraviolet absorber When the acrylic resin film is laminated on the base material for at least one purpose of protecting the base material, it is preferable to add an ultraviolet absorber to the acrylic resin film for imparting weather resistance.
- the molecular weight of the ultraviolet absorber is preferably 300 or more, and more preferably 400 or more.
- an ultraviolet absorber having a molecular weight of 300 or more is used, for example, when a film is produced, it is possible to suppress problems such as occurrence of roll contamination due to resin adhering to a transfer roll or the like.
- a benzotriazole type or triazine type having a molecular weight of 400 or more is more preferable. BASF Japan Co., Ltd.
- Tinuvin 360 Tinuvin 234, ADEKA Adeka Stab LA-31RG, BASF Japan Co., Ltd. Tinuvin 1577, Tinuvin 1600, ADEKA Adeka Stab LA- F70, ADK STAB LA-46 (all are trade names).
- a light stabilizer is added to the acrylic resin film.
- Known light stabilizers can be used, and radical scavengers such as hindered amine light stabilizers are particularly preferred.
- examples of such commercially available light stabilizers include Chimassorb 944, Chimassorb 2020, Tinuvin 770 from BASF Japan, and Adeka Stub LA-57G and Adeka Stub LA-72 from ADEKA (all are trade names).
- the weather resistance of the acrylic resin film can be enhanced by laminating an acrylic resin film molded by various molding methods on the surface thereof, that is, the surface opposite to the adhesive surface with the substrate.
- an acrylic resin film molded by various molding methods on the surface thereof, that is, the surface opposite to the adhesive surface with the substrate.
- a film composed of two or more layers of an acrylic resin and a fluororesin is laminated, further weather resistance and chemical resistance can be imparted.
- the fluororesin layer should be the outermost layer in terms of adhesion to the acrylic resin film and chemical resistance of the resulting molded product. Is preferred.
- the surface of the acrylic resin film can be subjected to surface treatment such as coating for imparting various functions, if necessary.
- Surface treatments for imparting functions include printing processes such as silk printing and inkjet printing, metal deposition for imparting metal tone or antireflection, sputtering, wet plating treatment, surface hardening treatment for improving surface hardness, and contamination prevention. Water repellent treatment or photocatalyst layer formation treatment, anti-dust treatment for the purpose of dust adhesion prevention or electromagnetic wave cut, antireflection layer formation, anti-glare treatment, and matte treatment.
- the one-sided printing process which prints on the single side
- back surface printing in which the printing surface is arranged on the adhesive surface with the substrate is preferable from the viewpoint of protecting the printing surface and imparting a high-class feeling.
- Example 1 [Production of rubber-containing multistage polymer (I) -1] Into a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen introduction tube, 195 parts of deionized water was added, then 0.3 parts of MMA, 4.7 parts of nBA and 0.08 parts of AMA, and OTP1 And a premixed mixture of 0.025 part of tBH were added and the temperature was raised to 75 ° C.
- Latex-like rubber-containing multistage polymers (I) -1 to 9 and (I) -101 to 104 are dropped into 100 parts of hot water at 70 ° C. containing 0.8 parts of calcium acetate to coagulate the latex. did. 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 acrylic resin composition.
- the test piece 1 was made up to a distance between chucks of 35 mm at the end point at a temperature of 23 ° C., an initial chuck distance of 25 mm, and a tensile speed of 500 mm / min in accordance with ISO 527.
- Tg of the elastic polymer The temperature corresponding to the peak appearing on the high temperature side was defined as Tg of the hard polymer (B).
- Example 11 [Production of rubber-containing multistage polymer (I) -11] After placing 195 parts of deionized water in a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen introduction tube, the monomers of the first elastic polymer (A1) shown in Table 2-3, etc. A premixed component was added and heated to 75 ° C. After raising the temperature, a mixture consisting 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 the polymerization vessel all at once to initiate the polymerization. . After confirming the temperature rise peak, the reaction was continued for 15 minutes to complete the polymerization of the first elastic polymer (A1).
- components such as a monomer of the second elastic polymer (A2) shown in Table 2-3 were dropped into the polymerization vessel over 150 minutes. Thereafter, the reaction was continued for 60 minutes to complete the polymerization of the second elastic polymer (A2). Subsequently, components such as monomers of the hard polymer (B) shown in Table 2-3 were dropped into the polymerization vessel over 120 minutes. Thereafter, the reaction was continued for 60 minutes to obtain latex-like multistage polymer (I) -11 containing rubber.
- 100 parts of the obtained latex-like rubber-containing multistage polymer (I) -11 was filtered with a filter having an opening of 50 ⁇ m and dropped into 100 parts of hot water at 80 ° C. containing 2.5 parts of calcium acetate, The latex was coagulated. 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 75 ° C. for 24 hours to obtain a powdery acrylic resin composition.
- Rubber-containing multistage polymers (I) 12 to 14 were produced in the same manner as in Example 11 except that the addition amounts shown in Table 2-3 were used. Thereafter, in the same manner as in Example 11, a powdery acrylic resin composition was obtained.
- LA-31RG UV absorber (manufactured by ADEKA)
- Tinuvin 234 UV absorber (manufactured by BASF Japan Ltd.)
- LA-57G Light stabilizer (manufactured by ADEKA Corporation) Chimassorb 2020: Light stabilizer (manufactured by BASF Japan Ltd.)
- Thermoplastic polymer (II) -1 Details are described later
- Irgnox 1076 Antioxidant (manufactured by BASF Japan Ltd.)
- Thermoplastic Polymer (II) -1 In a polymerization vessel equipped with a stirrer, a condenser, a thermocouple, and a nitrogen introduction tube, while stirring under nitrogen, 222 parts of deionized water, 3.9 parts of dipotassium alkenyl succinate, 80 parts of MMA, 20 parts of nBA and nOM 0.0008 The parts were charged all at once and the temperature was raised to 45 ° C. Furthermore, 6 parts of deionized water and 0.15 part of potassium persulfate were added all at once, and the temperature was raised to 55 ° C. Thereafter, the reaction was continued for 2.5 hours to obtain a latex-like thermoplastic polymer (II) -1.
- thermoplastic polymer (II) -1 This latex was dripped and coagulated in hot water containing calcium acetate. The coagulated product was separated and washed, and dried to obtain a thermoplastic polymer (II) -1. The reduced viscosity of the thermoplastic polymer (II) -1 was 0.82 dL / g.
- Thermoplastic Polymer (II) -2 In a polymerization vessel equipped with a stirrer, a condenser, a thermocouple, and a nitrogen introduction tube, while stirring under nitrogen, 143 parts of deionized water, 1.1 parts of dipotassium alkenyl succinate, 40 parts of MMA, 2 parts of nBA and nOM 0.0026 The parts were charged all at once and the temperature was raised to 50 ° C. Furthermore, 6 parts of deionized water and 0.15 part of potassium persulfate were added all at once, and the temperature was raised to 60 ° C.
- thermoplastic polymer (II) -2 was obtained. This latex was dripped and coagulated in hot water containing calcium acetate. The coagulated product was separated and washed, and dried to obtain a thermoplastic polymer (II) -2. The reduced viscosity of the thermoplastic polymer (II) -2 was 0.38 dL / g.
- LA-31RG UV absorber (manufactured by ADEKA)
- Tinuvin 234 UV absorber (manufactured by BASF Japan Ltd.)
- Tinuvin 1600 UV absorber (manufactured by BASF Japan Ltd.)
- Tinuvin 1577 UV absorber (manufactured by BASF Japan Ltd.)
- Thermoplastic polymer (II) -2 As stated above LA-57G: Light stabilizer (manufactured by ADEKA)
- Irgnox 1076 Antioxidant (manufactured by BASF Japan Ltd.)
- the acrylic resin compositions of Formulation Examples 21 to 24 have good weather resistance and good bleed-out resistance because they contain a UV absorber. For this reason, a molded article suitable for processing at room temperature can be obtained even for applications that require high designability. Moreover, since there is no bleed-out of additives and the like, the appearance is not deteriorated even after long-term storage. Molded bodies obtained from the acrylic resin compositions of Formulation Examples 21 to 24 are bonded to a base material such as a steel plate and then bent at room temperature to form the base material into various members such as a window frame. In this case, cracks do not occur at the curved portion. Therefore, the exposed base material is not corroded by being exposed to sunlight or the like.
- Examples 32 and 33 [Production of rubber-containing multistage polymer (I) -32, 33] A latex-like rubber-containing multistage polymer (I) -32, 33 was obtained in the same manner as in Example 31 except that the addition amount shown in Table 2 was used.
- Latex-like rubber-containing multistage polymer (I) was dropped into 100 parts of hot water at 70 ° C. containing 0.8 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 acrylic resin composition.
- Total light transmittance [1. Total light transmittance was measured in the same manner as [Total light transmittance].
- the acrylic resin composition of the present invention When the acrylic resin composition of the present invention is molded into a 1 mm-thick molded product, the total light transmittance is 90% or more and excellent in transparency, and is formed into a film by the molded product or the T-die method.
- the difference in whiteness ⁇ W before and after stretching of the obtained film was as small as 1 or less, and the stress whitening resistance was excellent (Examples 1 to 9).
- the acrylic resin composition of the present invention had a haze as small as 2%, and also had a good elongation at break at room temperature and low temperature.
- the Tg was 85 ° C. or higher
- the flexural modulus was 400 MPa or higher, and the flexibility was excellent.
- the acrylic resin composition (formulation) of the present invention to which various additives are added is excellent in transparency and stress whitening resistance, and has a low haze, flexural modulus, normal temperature and low temperature. The value of elongation at break was good (Formulation Examples 11 to 17).
- the acrylic resin composition (formulation) of the present invention to which certain additives were added was also excellent in bleed-out resistance (Formulation Examples 21 to 23). Therefore, by using the acrylic resin composition of the present invention, a decorative sheet or the like is bonded to a metal base material, and the base material is bent at room temperature or low temperature to form various members such as a front door.
- an acrylic resin molded body such as a highly designable film that does not cause problems such as cracking, peeling and whitening.
- This molded body is not exposed to cracks at the curved part when it is bonded to a base material such as a steel plate and then bent at room temperature to form this base material into various shapes such as window frames.
- the base material which became is not exposed to sunlight etc. and corroded.
- the obtained molded object has high heat resistance. For this reason, it is suitable for use in areas with high mechanical strength at high temperatures and strong sunlight at high temperatures.
- Molded products obtained by molding the acrylic resin composition of the present invention are agricultural vinyl houses, marking films, posters, wallpaper, foamed sheets, outdoor PVC leather, PVC steel roofing materials such as roofing materials and siding materials, It can be used as a coating material for water-related components in automobile interiors and exteriors, furniture replacement, elevator interiors, rain gutters, flooring, corrugated sheets, decorative pillars, lighting, bathrooms and kitchens. Moreover, it can be used also for the retardation film used for the polarizing film protective film used for polarizing plates, such as a heat insulation film and a liquid crystal display, the retardation film for viewing angle compensation, and phase difference compensation.
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Abstract
Description
〔1〕弾性重合体(A)を30質量%以上含有するゴム含有多段重合体(I)を含有するアクリル樹脂組成物であって、
(1)粉体状の前記アクリル樹脂組成物を加熱溶融させた後、温度200℃、圧力5MPaで5分間加圧し、次いで圧力2MPaをかけながら5分間冷却して製造される厚さ1mmの成形体の全光線透過率の値が90%以上であり、及び
(2)前記成形体からなる長さ80mm、幅15mmの試験片1、又は
前記アクリル樹脂組成物をTダイ法で製膜して得られる厚さ0.05~0.1mm、長さ80mm、幅15mmの試験片2、
をISO527に準拠して、初期チャック間距離を25mmとし、温度23℃において引張速度500mm/分で、終点のチャック間距離35mmまで10mm延伸した際の延伸前後の白色度の差ΔWが1以下である、
上記アクリル樹脂組成物。
〔2〕前記成形体のヘイズ値が2%以下である、前記〔1〕に記載のアクリル樹脂組成物。
〔3〕更に、前記アクリル樹脂組成物をTダイ法で製膜して得られた厚さ0.05~0.1mm、長さ150mm、幅15mmの試験片3が、下記条件(3)及び(4)を満たす、前記〔1〕又は〔2〕に記載のアクリル樹脂組成物;
(3):温度0℃で、引張速度50mm/分で延伸したときの破断伸度が20~300%、
(4):温度23℃で、引張速度50mm/分で延伸したときの破断伸度が100~500%。
〔4〕ゴム含有多段重合体(I)が、
炭素数1~8のアルキル基を有するアルキルアクリレート(a1)、及び、炭素数1~4のアルキル基を有するアルキルメタクリレート(a2)からなる群から選ばれる1種以上の単量体と、架橋性単量体(a4)とを含む単量体(a)を重合して得られる弾性重合体(A)、及び、
弾性重合体(A)の存在下で、炭素数1~4のアルキル基を有するアルキルメタクリレートを含む単量体(b)を重合して得られる硬質重合体(B)、
を含む重合体である、前記〔1〕~〔3〕のいずれかに記載のアクリル樹脂組成物。
〔5〕硬質重合体(B)のTgが85℃以上である、前記〔1〕~〔4〕のいずれかに記載のアクリル樹脂組成物。
〔6〕弾性重合体(A)がグラフト交叉剤を用いて製造されるグラフト重合体であって、弾性重合体(A)100質量%中の、グラフト交叉剤単位の含有率が1.3質量%以上である、前記〔1〕~〔5〕いずれかに記載のアクリル樹脂組成物。
〔7〕厚さ4mmの試験片について、ISO178に従って測定される曲げ応力から算出される曲げ弾性率が400MPa以上である、前記〔1〕~〔6〕のいずれかに記載のアクリル樹脂組成物。
〔8〕ASTM D-1238に従って測定される、温度230℃、荷重5.0kgの条件下でのMFR値が、1g/10分以上である、前記〔1〕~〔7〕のいずれかに記載のアクリル樹脂組成物。
〔9〕弾性重合体(A)中の、単量体(a1)単位と単量体(a2)単位の合計の含有率が80質量%以上である、前記〔1〕~〔8〕のいずれかに記載のアクリル樹脂組成物。
〔10〕弾性重合体(A)中の、単量体(a1)単位と単量体(a2)単位の合計質量を100としたときの単量体(a1)単位:単量体(a2)単位の質量比が、50:50~100:0である、前記〔1〕~〔9〕のいずれかに記載のアクリル樹脂組成物。
〔11〕硬質重合体(B)中の、単量体(b)単位の含有率が70質量%以上である、前記〔1〕~〔10〕のいずれかに記載のアクリル樹脂組成物。
〔12〕ゴム含有多段重合体(I)に対し、2-[2-ヒドロキシ-3,5-ビス(α,α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾール及び/又は2-[4,6-ビス(ビフェニル-4-イル)-1,3,5-トリアジン-2-イル]-5-[(2-エチルヘキシル)オキシ]フェノールを含有する、前記〔1〕~〔11〕のいずれかに記載のアクリル樹脂組成物。
〔13〕メチルメタクリレート単位50~100質量%と、メチルメタクリレートと共重合可能な1種以上の他のビニル単量体の単位0~50質量%とからなり、還元粘度が0.2~2dL/gである重合体からなる熱可塑性重合体(II)と、ゴム含有多段重合体(I)を含んでなる、前記〔1〕~〔12〕のいずれかに記載のアクリル樹脂組成物。
〔14〕炭素数1~8のアルキル基を有するアルキルアクリレート(a1)、及び、炭素数1~4のアルキル基を有するアルキルメタクリレート(a2)からなる群から選ばれる1種以上の単量体と、架橋性単量体(a4)とを含む単量体(a)を重合して弾性重合体(A)を得た後に、
弾性重合体(A)の存在下で、炭素数1~4のアルキル基を有するアルキルメタクリレートを含む単量体(b)を重合して硬質重合体(B)を得る、弾性重合体(A)及び硬質重合体(B)を含有するゴム含有多段重合体(I)の製造方法であって、
弾性重合体(A)100質量%中のグラフト交叉剤単位の含有率が1.3質量%以上であり、
ゴム含有多段重合体(I)100質量%中の弾性重合体(A)の含有率が30質量%以上である、上記ゴム含有多段重合体(I)の製造方法。
〔15〕下記の(5)~(7)を満たす、前記〔14〕に記載のゴム含有多段重合体(I)の製造方法;
(5):弾性重合体(A)中の、単量体(a1)単位と単量体(a2)単位の合計の含有率が80質量%以上、
(6):弾性重合体(A)中の、単量体(a1)単位/単量体(a2)単位の比率が、50~100質量%/0~50質量%、
(7):硬質重合体(B)中の、単量体(b)単位の含有率が70質量%以上。
〔16〕前記〔14〕又は前記〔15〕に記載の製造方法で得たゴム含有多段重合体(I)。
〔17〕前記〔16〕に記載のゴム含有多段重合体(I)を含有する、アクリル樹脂組成物。
〔18〕前記〔1〕~〔13〕のいずれか又は前記〔17〕に記載のアクリル樹脂組成物を成形して得た成形体。
〔19〕前記〔1〕~〔13〕のいずれか又は前記〔17〕に記載のアクリル樹脂組成物を成形して得たアクリル樹脂フィルム。
〔20〕前記〔1〕~〔13〕のいずれか又は前記〔17〕に記載のアクリル樹脂組成物をカレンダー加工により製膜するアクリル樹脂フィルムの製造方法。
〔21〕前記〔19〕に記載のアクリル樹脂フィルムを基材に積層した積層体。
〔22〕前記〔19〕に記載のアクリル樹脂フィルムを金属部材に積層した積層体。
(1)粉体状の前記アクリル樹脂組成物を加熱溶融させた後、温度200℃、圧力5MPaで5分間加圧し、次いで圧力2MPaをかけながら5分間冷却して製造した厚さ1mmの成形体の全光線透過率の値が90%以上であり、及び
(2)前記成形体からなる長さ80mm、幅15mmの試験片1、又は
前記アクリル樹脂組成物をTダイ法で製膜して得られた厚さ0.05~0.1mm、長さ80mm、幅15mmの試験片2、
をISO527に準拠して、初期チャック間距離を25mmとし、温度23℃において引張速度500mm/分で、終点のチャック間距離35mmまで10mm延伸した際の延伸前後の白色度の差ΔWが1以下である。
本発明のアクリル樹脂組成物は、それから成形される厚さ1mmのシート状成形物について、全光線透過率の値が90%以上であることを第1の特徴としている。全光線透過率は、ISO13468に準拠して測定される。
全光線透過率の測定に適する成形体としては、例えば、SUS板に挟んで温度200℃、圧力0MPaで10分間加熱溶融させた後、温度200℃、圧力5MPaで5分間加圧し、次いで圧力2MPaをかけながら5分間冷却して製造した厚さ1mmの成形体である。
厚さ1mm程度、あるいは0.05~0.1mmの基材を高速(500mm/分)で延伸することで白化ストレスが発現するかどうかを測定することができ、延伸前後の白色度Wの値の変化ΔW(延伸後白色度W2-延伸前白色度W1)が1以下であれば耐ストレス白化に優れていると判断できる。
白色度を測定するための試験片としては、本発明のアクリル樹脂組成物から製造される上記成形体(SUS板に挟んで温度200℃、圧力0MPaで10分間加熱溶融させた後、温度200℃、圧力5MPaで5分間加圧し、次いで圧力2MPaをかけながら5分間冷却して製造した厚さ1mmの成形体)を長さ80mm、幅15mmに切断して得られる試験片1、又は本発明のアクリル樹脂組成物をTダイ法で製膜して得られる厚さ0.05~0.1mmで、長さ80mm、幅15mmに切断して得られる試験片2が挙げられる。
W値とは白色度を数値化した値のことであり、耐ストレス白化性の指標値である。
引張試験前後のW値が1以下の場合、例えばフィルムを折曲加工した際に折り曲げた部分が白化しなかったり白化が目立たなかったりするため得られる成形品の外観が良好になる。
本発明のアクリル樹脂組成物から得られる成形体は、ヘイズ値が2%以下であることが好ましい。ヘイズ値の測定は、上記[全光線透過率]の場合と同様にして作成した厚さ1mmの成形体を、ヘイズ測定器、例えば、村上色彩技術研究所製ヘイズメーター(HR-100)を用いて、ISO14782に準拠して測定すればよい。
本発明のアクリル樹脂組成物は、該アクリル樹脂組成物をISO 527-3に従い、厚さ0.05~0.1mm、幅15mmに成形して得られたフィルムを試験片とし、(3):温度0℃で、引張速度50mm/分で延伸したときの破断伸度が20~300%であり、かつ(4):温度23℃で引張速度50mm/分の条件下で延伸した時の破断伸度が100~500%であることが好ましい。
0℃での破断伸度が20%以上の場合、例えば寒冷地や低温環境下でフィルムを延伸加工や曲げ加工する際にフィルムが破断しにくくなるため、加工性が良好となる。破断伸度が300%以下の場合、加工後のフィルムの余剰部分を切り取るとき等、取扱性が良好になる。0℃での破断伸度はより好ましくは30~300%、更に好ましくは40~300%である。
また、23℃での破断伸度が100%以上の場合、フィルムを延伸加工や曲げ加工する際にフィルムが破断することがないため、加工性が良好となる。破断伸度が500%以下の場合、加工後のフィルムの余剰部分を切り取るとき等、取扱性が良好になる。23℃での破断伸度はより好ましくは120~500%、更に好ましくは130~500%である。
本発明のアクリル樹脂組成物は、それから成形される厚さ4mmの試験片が、400MPa以上の曲げ弾性率を示すことが好ましい。
より詳細には、ISO178に従って、厚さ4mm、長さ80mm、幅10mmの寸法の試験片について、温度23℃、支点間距離64mm、試験速度2mm/分で、試験片の中央に荷重を掛けてたわみ量が0.088mmと0.44mmとなる時の曲げ応力から算出される、曲げ弾性率の値が400MPa以上であることが好ましい。曲げ弾性率が400MPa以上であれば、樹脂に適度な強度を付与することができ、製造時、あるいは施工時に安定した性能を発揮する。成形体の曲げ弾性率を上記の範囲内にするための手段として、ゴム含有多段重合体(I)の弾性重合体(A)100質量%中に含まれる架橋性単量体(a4)(後述)中のグラフト交叉剤単位の量を1.3質量%以上とすることが有効である。
本発明のアクリル樹脂組成物は、ASTM D-1238に従い、温度230℃、荷重5.0kgの条件下で測定したMFR値が、1g/10分以上であることが好ましい。
MFRは成形加工性の指標値であり、1g/10分以上であると、成形加工時に樹脂の滞留が起きにくいため好ましい。
本発明のアクリル樹脂組成物は、弾性重合体(A)を30質量%以上含有するゴム含有多段重合体(I)を含有する。
ゴム含有多段重合体(I)は、炭素数1~8のアルキル基を有するアルキルアクリレート(a1)及び炭素数1~4のアルキル基を有するアルキルメタクリレート(a2)からなる群より選ばれる1種以上の単量体と、架橋性単量体(a4)とを含む単量体(a)を重合して得られる弾性重合体(A)、及び該弾性重合体(A)の存在下で、炭素数1~4のアルキル基を有するアルキルメタクリレートを含む単量体(b)を重合して得られる硬質重合体(B)を含む、ゴム含有多段重合体であることが好ましい。
弾性重合体(A)の原料として用いられる炭素数1~8のアルキル基を有するアルキルアクリレート(a1)(以下、「単量体(a1)」又は「アルキルアクリレート(a1)」という場合がある。)は、直鎖状、分岐状の何れでもよい。その具体例としては、メチルアクリレート、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、2-エチルヘキシルアクリレート、n-オクチルアクリレートが挙げられる。これらは一種を単独で又は二種以上を組み併せて用いてもよい。特に、ガラス転移温度(Tg)が低いアルキルアクリレートが好ましく、n-ブチルアクリレートがより好ましい。Tgが低ければ、弾性重合体(A)が良好な耐衝撃性を有し、かつ容易に成形できる。
弾性重合体(A)中の、単量体(a1)単位/単量体(a2)単位の比率は、単量体(a1)単位と単量体(a2)単位の合計質量を100としたとき、単量体(a1)単位:単量体(a2)単位の質量比が50:50~100:0であることが好ましい。
グラフト交叉剤は主としてそのエステルの共役不飽和結合がアリル基、メタリル基又はクロチル基よりはるかに早く反応し、化学的に結合する。その間、グラフト交叉剤中のアリル基、メタリル基又はクロチル基の実質上の大部分は、反応せずに残存し、次層重合体の重合中に反応して、隣接二層間にグラフト結合を与える。
尚、この架橋性単量体(a4)は、上述のように得られる成形体にゴム弾性を付与したり、グラフト交叉を生じるような単量体に限定されない。例えば耐熱性等が厳しく要求される場合等、成形体の使用目的に応じて他の単量体を用いることができる。例えば、エチレングリコールジメタクリレート、1,3-ブチレングリコールジメタクリレート、1,4-ブチレングリコールジメタクリレート、プロピレングリコールジメタクリレート等のアルキレングリコールジメタクリレートが挙げられる。また、ジビニルベンゼン、トリビニルベンゼン等のポリビニルベンゼンも使用できる。
架橋性単量体(a4)中のグラフト交叉剤の量は、アクリル樹脂に充分な軟質性を与えるという観点からは、単量体(a)100質量%中、3.0質量%以下が好ましく、1.3質量%以下がより好ましい。グラフト交叉剤の量が3.0質量%以下であれば、弾性重合体(A)と硬質重合体(B)との間の架橋が強固とならず、アクリル樹脂に充分な軟質性が発現する。
架橋性単量体(a4)中グラフト交叉剤中のグラフト交叉剤の量は、単量体(a)100質量%中、1.3質量%以上が好ましく、1.6質量%以上がより好ましい。上限値は特に限定されないが、例えば、6.0質量%以下程度である。グラフト交叉剤の量が1.3質量%以上であれば、弾性重合体(A)と硬質重合体(B)との間の架橋が安定となり、充分な透明性が発現する。また、ゴム弾性をより向上でき、得られる成形体の耐衝撃性が増大する。
弾性重合体(A)のTgは0℃以下が好ましく、-30℃以下がより好ましい。Tgが0℃以下であれば、得られる成形体が好ましい耐衝撃性を有する。
このTgは、動的粘弾性測定装置を用いて次のように測定される値である。先ず、アクリル樹脂組成物を溶融して、厚さ1mm、幅6mmのシートに成形し、次いで厚さ1mm、幅6mm、長さ65mmの寸法の試験片を得る。動的粘弾性測定装置を用いて、ISO6721-4に準拠して、初期チャック間距離2cm、測定周波数0.1Hz、測定温度範囲-90~150℃、昇温速度2℃/分、窒素気流200mL/分の条件で、引張モードで、該試験片の貯蔵弾性率(E')と損失弾性率(E'')の値を測定し、『tanδ=E''/E'』の式にしたがって各温度におけるtanδ(損失正接)の値を算出する。次にtanδの値を温度に対してプロットすると、二つ以上のピークが現れる。このうちの最も低温側に現れるピークに対応する温度を弾性重合体(A)のTgとする。
ゴム含有多段重合体(I)は、以上説明した弾性重合体(A)の存在下で、炭素数1~4のアルキル基を有するアルキルメタクリレート(b1)を含む単量体(b)を重合することにより得ることが好ましい。単量体(b)は重合により硬質重合体(B)を形成することができる。
硬質重合体(B)のTgは85℃以上であることが好ましく、より好ましくは90℃以上である。このようなTgを有することにより、成形性に優れるアクリル樹脂組成物が得られ、かつ成形体の耐熱性が高く、高温下での機械的強度が大きく、高温で太陽光が強い地域でも良好に使用可能となる。
硬質重合体(B)のTgは、前述のゴム含有多段重合体(I)の動的粘弾性測定において、最も高温側(80℃以上)に現れるピークに対応する温度である。
また、弾性重合体(A)の重合反応終了後、単量体(b)の重合を行なう前に、弾性重合体(A)を構成する単量体の組成から、炭素数1~8のアルキル基を有するアルキルアクリレートの含有量を徐々に減じ、炭素数1~4のアルキル基を有するアルキルメタクリレートの含有量を徐々に増加させた組成の単量体を順次重合して中間部重合体(C)を形成することもできる。
乳化重合法を用いた場合、重合反応終了後のラテックスからゴム含有多段重合体(I)を粉体として回収することが好ましい。粉体として回収する方法としては、例えば、ラテックスを凝固剤と接触させて凝固あるいは塩析し、固液分離し、重合体の1~100質量倍程度の水で洗浄し、濾別等の脱水処理により湿潤状の粉体とし、更に、この湿潤状の粉体を圧搾脱水機や流動乾燥機等の熱風乾燥機で乾燥させる方法がある。その他、スプレードライ法によりラテックスを直接乾燥させてもよい。重合体の乾燥温度、乾燥時間は重合体の種類によって適宜決定できる。
[1]ゴム含有多段重合体(I)1gをアセトン50gに溶解させ、70℃で4時間還流させてアセトン可溶分を得る。
[2]得られた抽出液を、CRG SERIES((株)日立製作所製)を用いて、4℃において14000rpmで30分間遠心分離を行なう。
[3]アセトン不溶分をデカンテーションで取り除き、真空乾燥機にて50℃で、24時間乾燥させて得られたアセトン可溶分について、以下の条件でGPC測定を行ない、標準ポリスチレンによる検量線から質量平均分子量を求める。
装置:東ソー(株)製「HLC8220」、
カラム:東ソー(製)「TSKgel SuperMultiporeHZ-H」(内径4.6mm×長さ15cm×2本、排除限界4×107(推定))、
溶離液:テトラヒドロフラン(THF)、
溶離液流量:0.35ml/分、
測定温度:40℃、
試料注入量 10μl(試料濃度0.1%)。
本発明のアクリル樹脂組成物は、ゴム含有多段重合体(I)と、更に熱可塑性重合体(II)を含有していてもよい。
本発明に好ましく用いられる熱可塑性重合体(II)は、メチルメタクリレート単位50~100質量%と、これと共重合可能な1種以上のビニル単量体単位0~50質量%とからなる還元粘度が0.2~2dL/gである重合体である。熱可塑性重合体(II)を用いることにより、アクリル樹脂組成物の成形性を向上できる。すなわち熱可塑性重合体(II)を配合することによって、アクリル樹脂組成物のメルトテンションが上昇するので、フィルム状に溶融押出する場合には、吐出量が低下して生産性が悪化することを防止でき、更にはフィルム等の成形体の厚み精度も向上できる。
シアン化ビニル単量体の具体例としては、アクリロニトリル、メタクリロニトリルが挙げられる。
メチルメタクリレート以外のアルキルメタクリレートの具体例としては、エチルメタクリレート、プロピルメタクリレート、ブチルメタクリレートが挙げられる。
アルキルメタクリレートの具体例としては、ブチルメタクリレートが挙げられる。
アルキルアクリレートの具体例としては、先に説明した弾性重合体(A)に用いるアルキルアクリレート(a1)の具体例と同じである。
2-[2-ヒドロキシ-3,5-ビス(α,α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾール及び/又は2-[4,6-ビス(ビフェニル-4-イル)-1,3,5-トリアジン-2-イル]-5-[(2-エチルヘキシル)オキシ]フェノールの含有量は、ゴム含有多段重合体(I)100質量部に対し、0.5~5質量部であることが好ましく、より好ましくは1~3質量部である。
また、粉体で回収された熱可塑性重合体(II)も上述のゴム含有多段重合体(I)等とミキサー等で混合し、それらを押出混練、ロール混練等の方法で溶融混合することによって得ることができる。
また、ゴム含有多段重合体(I)と熱可塑性重合体(II)を各々乳化重合によって得る場合は、ゴム含有多段重合体(I)の重合反応終了後のラテックスと熱可塑性重合体(II)の重合反応終了後のラテックスとを混合し、その後両重合体を含む粉体を回収することによって本発明のアクリル樹脂組成物を得ることもできる。
また、アクリル樹脂組成物を溶融押出成形する場合は、まずゴム含有多段重合体(I)の全量の内の一部、2-[2-ヒドロキシ-3,5-ビス(α,α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾール及び/又は2-[4,6-ビス(ビフェニル-4-イル)-1,3,5-トリアジン-2-イル]-5-[(2-エチルヘキシル)オキシ]フェノール、熱可塑性重合体(II)、及び必要に応じて配合剤を混合して単軸押出機又は二軸押出機に供給し、溶融混練してマスターバッチペレットを作製し、このマスターバッチペレットとゴム含有多段重合体(I)の残部とを混合して再び単軸押出機又は二軸押出機に供給し、溶融混練、溶融押出を行ない、成形体を得ることもできる。
本発明のアクリル樹脂組成物を成形して得られる成形体は、フィルム、シート、三次元構造体等の何れの形状であってもよい。特にフィルム状の成形体が好ましい。このような成形体の用途としては、例えば、農業用ビニルハウス、マーキングフィルム、ポスター、壁紙、発泡シート、屋外用塩ビレザー、塩ビ鋼板の屋根材及びサイディング材等の外壁建材、自動車内外装、家具等の塗装代替、エレベーター内装、雨樋、床材、波板、化粧柱、照明、浴室や台所等の水周り部材の被膜材が挙げられる。その他、断熱フィルム、液晶ディスプレイ等の偏光板に使用される偏光膜保護フィルム、視野角補償、位相差補償のための位相差板に使用される位相差フィルムにも使用できる。ここで「フィルム状の成形体」とは、シートも含むものとする。
本発明のアクリル樹脂フィルムは、そのままで各種用途に使用してもよく、基材に積層して使用してもよい。この透明なアクリル樹脂フィルムを基材に積層すれば、クリア塗装の代替となり、基材の色調を生かすことができる。このように基材の色調を生かす用途において、アクリル樹脂フィルムは、ポリ塩化ビニルフィルムやポリエステルフィルムに比べて、透明性、深み感、高級感の点で優れている。基材としては、例えば、各種樹脂又は鋼板等の金属からなる成形品、木工製品が挙げられる。基材を構成する樹脂は、アクリル樹脂フィルムと溶融接着可能な熱可塑性樹脂であることが好ましい。この熱可塑性樹脂の具体例としては、アクリロニトリル-ブタジエン-スチレン(ABS)樹脂、アクリロニトリル-スチレン(AS)樹脂、ポリスチレン樹脂、ポリカーボネート樹脂、塩化ビニル樹脂、アクリル樹脂、ポリエステル樹脂あるいはこれらを主成分とする樹脂が挙げられる。中でも、接着性の点から、ABS樹脂、AS樹脂、ポリカーボネート樹脂、塩化ビニル樹脂あるいはこれらの樹脂を主成分とする樹脂が好ましい。また、ポリオレフィン樹脂等の溶融接着し難い樹脂からなる基材の場合は、適宜接着層を設けてからアクリル樹脂フィルムを積層してもよい。
実施例中の略号は、表1に示す材料を意味する。
[ゴム含有多段重合体(I)-1の作製]
攪拌機、冷却管、熱電対、窒素導入管を備えた重合容器内に、脱イオン水195部を投入後、MMA0.3部、nBA4.7部及びAMA0.08部の単量体成分、及びOTP1部、tBH0.025部を予備混合したものを投入し、75℃に昇温した。
昇温後、脱イオン水5部、ソジウムホルムアルデヒドスルホキシレート0.2部、硫酸第一鉄0.0001部及びEDTA0.0003部からなる混合物を一度に投入し、重合を開始した。ピーク温度確認後、15分間反応を継続させ、第一弾性重合体(A1)の重合を完結した。
[ゴム含有多段重合体(I)-2~9、(I)-101~103の作製]
表2-1、表2-2、表2-5に記載の添加量としたこと以外は、実施例1と同様にして、ラテックス状のゴム含有多段重合体(I)-2~9、(I)-101~103を得た。
[ゴム含有多段重合体(I)-104の作製]
製造途中、表2-5に示した中間重合体(C)の単量体等の成分を45分間に亘って重合容器内に滴下し、その後60分間反応を維持したこと、及び、表2-5に記載の添加量としたこと以外は、実施例1と同様にして、ラテックス状のゴム含有多段重合体(I)-104を得た。
ラテックス状のゴム含有多段重合体(I)-1~9及び(I)-101~104を、酢酸カルシウム0.8部を含む70℃の熱水100部中に滴下して、ラテックスを凝析した。更に、95℃に昇温して5分保持し、固化した。得られた凝析物を分離洗浄し、70℃で24時間乾燥して、粉体状アクリル樹脂組成物を得た。
得られた粉体状アクリル樹脂組成物について、以下の各評価を実施し、表3及び表4に示す結果を得た。
庄司鉄工(株)製プレス成形機を用いて、粉体状アクリル樹脂組成物をSUS板に挟んで温度200℃、圧力0MPaで10分間加熱溶融させた後、温度200℃、圧力5MPaで5分間加圧した。次いで圧力2MPaをかけながら5分間冷却し、厚さ1mmの成形体を得た。
これを試験片とし、村上色彩技術研究所製ヘイズメーター(HR-100)を用いて、ISO13468に準拠して全光線透過率を測定した。
前記[1.全光線透過率]の場合と同様にして厚さ1mmの成形体を得た。これを試験片とし、村上色彩技術研究所製ヘイズメーター(HR-100)を用いて、ISO14782に準拠してヘイズを測定した。
前記[1.全光線透過率]の場合と同様にして厚さ1mmの成形体を得た。この成形体を長さ80mm、幅15mmに切断して試験片1を作製した。
試験片1について、日本電色工業(株)製分光式色差計SE-2000を用いて白色度W1の値を測定した。
次に、東洋精機製作所(株)製ストログラフTを用いて、ISO527に準拠して温度23℃、初期チャック間距離25mm、引張速度500mm/分で終点のチャック間距離35mmまで、試験片1を引張った後、日本電色工業(株)製分光式色差計SE-2000を用いて白色度W2の値を測定した。
引張試験前後の白色度の差 ΔW(=W2―W1)を求めた。
前記[1.全光線透過率]の場合と同様にして厚さ1mmの成形体を得た。この成形体を幅6mmに切断して試験片を作成した。
セイコーインスツルメンツ(株)製動的粘弾性測定装置EXSTAR DMS6100を用いて、ISO6721-4に準拠して、初期チャック間距離20mm、測定周波数0.1Hz、測定温度範囲-90~150℃、昇温速度2℃/分、窒素気流200mL/分下で、引張モードで測定した貯蔵弾性率(E’)と損失弾性率(E’’)の値を用いて、『tanδ=E’’/E’』の式に従って各温度においてtanδ(損失正接)の値を算出した。
次にtanδの値を温度に対してプロットすると、二つのピークが現れた。このうちの低温側に現れたピークに対応する温度を弾性重合体のTgとした。また高温側に現れたピークに対応する温度を硬質重合体(B)のTgとした。
前記[1.全光線透過率]の場合と同様にして、但し厚さは4mmで、成形体を得た。この成形体を長さ80mm、幅10mmに切断し、試験片を作成した。
東洋精機製作所(株)製ストログラフTを用いて、ISO178に準拠して温度23℃、支点間距離64mm、試験速度2mm/分で曲げ試験をし、たわみ0.088mmと0.44mmで測定した曲げ応力から曲げ弾性率を算出した。
[ゴム含有多段重合体(I)-11の作製]
撹拌器、冷却管、熱電対、窒素導入管を備えた重合容器に、脱イオン水195部を入れた後、表2-3に示した第一弾性重合体(A1)の単量体等の成分を予備混合したものを投入し、75℃に昇温した。
昇温後、脱イオン水5部、ソジウムホルムアルデヒドスルホキシレート0.2部、硫酸第一鉄0.0001部及びEDTA0.0003部からなる混合物を重合容器へ一度に投入し、重合を開始した。温度上昇ピークを確認後、15分間反応を継続させ、第一弾性重合体(A1)の重合を完結した。
続いて、表2-3に示した硬質重合体(B)の単量体等の成分を120分間に亘って重合容器内に滴下した。その後60分間反応を継続させ、ラテックス状のゴム含有多段重合体(I)-11を得た。
[ゴム含有多段重合体(I)12~14の作製]
表2-3に記載の添加量としたこと以外は、実施例11と同様にして、ゴム含有多段重合体(I)12~14を作製した。
その後、実施例11と同様にして、粉体状アクリル樹脂組成物を得た。
[ゴム含有多段重合体(I)-15~17、(I)-111の作製]
製造途中、表2-3及び表2-5に示した中間重合体(C)の単量体等の成分を45分間に亘って重合容器内に滴下し、その後60分間反応を維持したこと、及び、表2-3及び表2-5に記載の添加量としたこと以外は、実施例11と同様にして、ゴム含有多段重合体(I)-15~17、(I)-111を作製した。
その後、実施例11と同様にして、粉体状アクリル樹脂組成物を得た。
得られた粉体状アクリル樹脂組成物を用い、表5に示す配合で、紫外線吸収剤、光安定剤、抗酸化剤等の各種助剤を、ヘンシェルミキサーを用いて混合し、この粉体混合物を脱気式押出機(TEM-35:東芝機械(株)製)を用いてシリンダー温度100~240℃、ダイ温度240℃で溶融混練してペレットを得た。
続いて、上記ペレットを80℃で一昼夜乾燥し、300mm幅のTダイを取り付けた40mm口径のノンベントスクリュー型押し出し機(L/D=26)を用いてシリンダー温度200~240℃、Tダイ温度250℃、冷却ロール温度80℃で厚さ0.05~0.1mmのフィルムを成形した。
LA-31RG :紫外線吸収剤((株)ADEKA製)
Tinuvin234 :紫外線吸収剤(BASFジャパン(株)製)
LA-57G :光安定剤 ((株)ADEKA製)
Chimassorb2020 :光安定剤 (BASFジャパン(株)製)
熱可塑性重合体(II)-1 :詳細は後述
熱可塑性重合体(II)-2 :詳細は後述
アエロジルR976 :ブロッキング防止剤(日本アエロジル(株)製)
Irgnox1076 :抗酸化剤(BASFジャパン(株)製)
攪拌機、冷却管、熱電対、窒素導入管を備えた重合容器内に、窒素下で撹拌しながら、脱イオン水222部、アルケニルコハク酸ジカリウム3.9部、MMA80部、nBA20部及びnOM0.0008部を一括で投入し、45℃に昇温した。
更に、脱イオン水6部及び過硫酸カリウム0.15部を一括で投入し、55℃に昇温した。その後、2.5時間反応を継続させ、ラテックス状の熱可塑性重合体(II)-1を得た。
このラテックスを、酢酸カルシウムを含む熱水中に滴下して凝析した。凝析物を分離洗浄し、乾燥して、熱可塑性重合体(II)-1を得た。
熱可塑性重合体(II)-1の還元粘度は0.82dL/gであった。
攪拌機、冷却管、熱電対、窒素導入管を備えた重合容器内に、窒素下で撹拌しながら、脱イオン水143部、アルケニルコハク酸ジカリウム1.1部、MMA40部、nBA2部及びnOM0.0026部を一括で投入し、50℃に昇温した。
更に、脱イオン水6部及び過硫酸カリウム0.15部を一括で投入し、60℃に昇温した。その後、反応を継続させ、温度が一旦昇温した後、70℃まで低下したところで、MMA44部、nBA14部及びnOM0.0087部を、90分間に亘って滴下し、2時間反応を継続させ、ラテックス状の熱可塑性重合体(II)-2を得た。
このラテックスを、酢酸カルシウムを含む熱水中に滴下して凝析した。凝析物を分離洗浄し、乾燥して、熱可塑性重合体(II)-2を得た。
熱可塑性重合体(II)-2の還元粘度は0.38dL/gであった。
以下の各評価を実施し、表6及び表7に示す結果を得た。
配合例11~17、比較配合例11で調製した粉体混合物を用い、前記[1.全光線透過率]と同様にして、全光線透過率を測定した。
配合例11~17、比較配合例11で調製した粉体混合物を用い、前記[1.ヘイズ]と同様にして、ヘイズを測定した。
Tダイ法で製膜して得られた厚さ0.05~0.1mmのフィルムを幅15mmに切断し、試験片2を作製した。
試験片2を用い、前記[1.白色度(ΔW)]と同様にして、白色度の差 ΔW(=W2―W1)を求めた。
配合例11~17、比較配合例11で調製した粉体混合物を用い、Tダイ法で製膜して得られたフィルムを、ISO 527-3に従い、厚さ0.05~0.1mm、幅15mmに成形して、これを試験片3とした。
条件(1):試験片3を、温度0℃で引張速度50mm/分の条件下で延伸したときの破断伸度を、表5の「破断伸度%MD/TD」(0℃)の行に示した。
条件(2):試験片3を、温度23℃で引張速度50mm/分の条件下で延伸したときの破断伸度を、表5の「破断伸度%MD/TD」(23℃)の行に示した。
配合例11~17、比較配合例11で調製した粉体混合物を用い、ASTM D-1238に従い、温度230℃、荷重5.0kgの条件下でのMFR値を測定した。
前記の、ゴム含有多段重合体(I)-11の粉体状アクリル樹脂組成物を用い、表8に示す配合で、紫外線吸収剤、光安定剤、抗酸化剤等の各種助剤を、ヘンシェルミキサーを用いて混合し、この粉体混合物を脱気式押出機(TEM-35:東芝機械(株)製)を用いてシリンダー温度100~240℃、ダイ温度240℃で溶融混練してペレットを得た。
続いて、上記ペレットを80℃で一昼夜乾燥し、300mm幅のTダイを取り付けた40mm口径のノンベントスクリュー型押し出し機(L/D=26)を用いてシリンダー温度220~250℃、Tダイ温度250℃、冷却ロール温度80℃で厚さ0.05mmのフィルムを成形した。
LA-31RG :紫外線吸収剤((株)ADEKA製)
Tinuvin234 :紫外線吸収剤(BASFジャパン(株)製)
Tinuvin1600 :紫外線吸収剤(BASFジャパン(株)製)
Tinuvin1577 :紫外線吸収剤(BASFジャパン(株)製)
熱可塑性重合体(II)-2 :既述
LA-57G :光安定剤 ((株)ADEKA製)
Irgnox1076 :抗酸化剤(BASFジャパン(株)製)
以下の各評価を実施し、表9に示す結果を得た。
得られた粉体混合物を用い、前記[1.全光線透過率]と同様にして、全光線透過率を測定した。
配合例11と同じく、ゴム含有多段重合体(I)-11を用いた評価であるため、全光線透過率の測定結果は配合例11と同じであった。
得られた粉体混合物を用い、前記[1.ヘイズ]と同様にして、ヘイズを測定した。
配合例11と同じく、ゴム含有多段重合体(I)-11を用いた評価であるため、ヘイズの測定結果は配合例11と同じであった。
得られた粉体混合物を用い、前記[1.白色度(ΔW)]と同様にして、白色度(ΔW)を求めた。
配合例11と同じく、ゴム含有多段重合体(I)-11を用いた評価であるため、白色度(ΔW)の測定結果は配合例11と同じであった。
Tダイ法で製膜して得られたフィルムを、80℃、90RH%で10時間の条件で加湿加温してブリードアウトの有無を目視で評価した。
○:ブリードアウトがなく、フィルムが曇っていない。
×:ブリードアウトが見られ、フィルムが白く曇っている。
配合例21~24のアクリル樹脂組成物から得られる成形体は、鋼板等の基材に貼り合わせた後、この基材を窓枠等の各種部材の形状にするために、常温で曲げ加工する際に、曲部でクラックが発生しない。従って、剥き出しになった基材が太陽光等に曝されて腐蝕することがない。
[ゴム含有多段重合体(I)-31の作製]
攪拌機、冷却管、熱電対、窒素導入管を備えた重合容器内に、脱イオン水195部を投入後、MMA0.3部、nBA4.7部及びAMA0.03部の単量体成分、及びOTP1部、tBH0.013部を予備混合したものを投入し、75℃に昇温した。昇温後、脱イオン水5部、ソジウムホルムアルデヒドスルホキシレート0.20部、硫酸第一鉄0.0001部及びEDTA0.0003部からなる混合物を一度に投入し、重合を開始した。ピーク温度確認後、15分間反応を継続させ、第一弾性重合体(A1)の重合を完結した。
[ゴム含有多段重合体(I)-32,33の作製]
表2に記載の添加量としたこと以外は、実施例31と同様にして、ラテックス状のゴム含有多段重合体(I)-32,33を得た。
ラテックス状のゴム含有多段重合体(I)を、酢酸カルシウム0.8部を含む70℃の熱水100部中に滴下して、ラテックスを凝析した。更に、95℃に昇温して5分保持し、固化した。得られた凝析物を分離洗浄し、70℃で24時間乾燥して、粉体状アクリル樹脂組成物を得た。
以下の各評価を実施し、表10に示す結果を得た。
前記[1.全光線透過率]と同様にして、全光線透過率を測定した。
前記[1.白色度(ΔW)]と同様にして、白色度(ΔW)を求めた。
ゴム含有多段重合体(I)のアセトン可溶分の質量平均分子量を、測定した。
測定方法は、本文中に記載の通りである。
前記[1.曲げ弾性率]と同様にして、曲げ弾性率を測定した。
本発明のアクリル樹脂組成物は、厚さ1mmの成形体に成形した場合、全光線透過率が90%以上であり透明性に優れ、また、前記成形体、又はTダイ法で成膜して得有られるフィルムの延伸前後の白色度の差ΔWが1以下と小さく、耐ストレス白化性に優れていた(実施例1~9)。
また、本発明のアクリル樹脂組成物は、ヘイズが2%と小さく、更に、常温及び低温下での破断伸度の値が良好であった。更に、Tgが85℃以上であり、曲げ弾性率がいずれも400MPa以上であって柔軟性に優れていた。
様々な添加剤を添加した本発明のアクリル樹脂組成物(配合物)についても同様に、透明性、耐ストレス白化性が優れており、更に、ヘイズが小さく、曲げ弾性率、常温及び低温下での破断伸度の値が良好であった(配合例11~17)。
また、一定の添加剤を添加した本発明のアクリル樹脂組成物(配合物)は、耐ブリードアウト性においても優れていた(配合例21~23)。
従って本発明のアクリル樹脂組成物を用いることにより、化粧シート等を金属製の基材に貼り合わせ、この基材を玄関ドア等の各種部材の形状にするために常温又は低温で曲げ加工を施しても割れや剥れ、白化等の問題が生じることがない意匠性の高いフィルム等のアクリル樹脂成形体を製造することができる。
この成形体は、鋼板等の基材に貼り合わせた後、この基材を窓枠等の各種部材の形状にするために常温曲げ加工する際に曲部でクラックが発生せず、このため剥き出しになった基材が太陽光等に曝され腐蝕することがない。また得られる成形体は耐熱性が高い。このため高温下での機械的強度が大きく、高温で太陽光が強い地域での使用に好適である。
Claims (22)
- 弾性重合体(A)を30質量%以上含有するゴム含有多段重合体(I)を含有するアクリル樹脂組成物であって、
(1)粉体状の前記アクリル樹脂組成物を加熱溶融させた後、温度200℃、圧力5MPaで5分間加圧し、次いで圧力2MPaをかけながら5分間冷却して製造される厚さ1mmの成形体の全光線透過率の値が90%以上であり、及び
(2)前記成形体からなる長さ80mm、幅15mmの試験片1、または
前記アクリル樹脂組成物をTダイ法で製膜して得られる厚さ0.05~0.1mm、長さ80mm、幅15mmの試験片2、
をISO527に準拠して、初期チャック間距離を25mmとし、温度23℃において引張速度500mm/分で、終点のチャック間距離35mmまで10mm延伸した際の延伸前後の白色度の差ΔWが1以下である、
上記アクリル樹脂組成物。 - 前記成形体のヘイズ値が2%以下である、請求項1に記載のアクリル樹脂組成物。
- 更に、前記アクリル樹脂組成物をTダイ法で製膜して得られた厚さ0.05~0.1mm、長さ150mm、幅15mmの試験片3が、下記条件(3)及び(4)を満たす、請求項1に記載のアクリル樹脂組成物;
(3):温度0℃で、引張速度50mm/分で延伸したときの破断伸度が20~300%、
(4):温度23℃で、引張速度50mm/分で延伸したときの破断伸度が100~500%。 - ゴム含有多段重合体(I)が、
炭素数1~8のアルキル基を有するアルキルアクリレート(a1)、及び、炭素数1~4のアルキル基を有するアルキルメタクリレート(a2)からなる群から選ばれる1種以上の単量体と、架橋性単量体(a4)とを含む単量体(a)を重合して得られる弾性重合体(A)、及び、
弾性重合体(A)の存在下で、炭素数1~4のアルキル基を有するアルキルメタクリレートを含む単量体(b)を重合して得られる硬質重合体(B)、
を含む重合体である、請求項1に記載のアクリル樹脂組成物。 - 硬質重合体(B)のTgが85℃以上である、請求項1に記載のアクリル樹脂組成物。
- 弾性重合体(A)がグラフト交叉剤を用いて製造されるグラフト重合体であって、弾性重合体(A)100質量%中の、グラフト交叉剤単位の含有率が1.3質量%以上である、請求項1に記載のアクリル樹脂組成物。
- 厚さ4mmの試験片について、ISO178に従って測定される曲げ応力から算出される曲げ弾性率が400MPa以上である、請求項1に記載のアクリル樹脂組成物。
- ASTM D-1238に従って測定される、温度230℃、荷重5.0kgの条件下でのMFR値が、1g/10分以上である、請求項1に記載のアクリル樹脂組成物。
- 弾性重合体(A)中の、単量体(a1)単位と単量体(a2)単位の合計の含有率が80質量%以上である、請求項1に記載のアクリル樹脂組成物。
- 弾性重合体(A)中の、単量体(a1)単位と単量体(a2)単位の合計質量を100としたときの、単量体(a1)単位:単量体(a2)単位の質量比が50:50~100:0である、請求項1に記載のアクリル樹脂組成物。
- 硬質重合体(B)中の、単量体(b)単位の含有率が70質量%以上である、請求項1に記載のアクリル樹脂組成物。
- ゴム含有多段重合体(I)に対し、2-[2-ヒドロキシ-3,5-ビス(α,α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾール及び/又は2-[4,6-ビス(ビフェニル-4-イル)-1,3,5-トリアジン-2-イル]-5-[(2-エチルヘキシル)オキシ]フェノールを含有する、請求項1に記載のアクリル樹脂組成物。
- メチルメタクリレート単位50~100質量%と、メチルメタクリレートと共重合可能な1種以上の他のビニル単量体の単位0~50質量%とからなり、還元粘度が0.2~2dL/gである重合体からなる熱可塑性重合体(II)と、ゴム含有多段重合体(I)を含んでなる、請求項1に記載のアクリル樹脂組成物。
- 炭素数1~8のアルキル基を有するアルキルアクリレート(a1)、及び、炭素数1~4のアルキル基を有するアルキルメタクリレート(a2)からなる群から選ばれる1種以上の単量体と、架橋性単量体(a4)とを含む単量体(a)を重合して弾性重合体(A)を得た後に、
弾性重合体(A)の存在下で、炭素数1~4のアルキル基を有するアルキルメタクリレートを含む単量体(b)を重合して硬質重合体(B)を得る、弾性重合体(A)及び硬質重合体(B)を含有するゴム含有多段重合体(I)の製造方法であって、
弾性重合体(A)100質量%中のグラフト交叉剤単位の含有率が1.3質量%以上であり、
ゴム含有多段重合体(I)100質量%中の弾性重合体(A)の含有率が30質量%以上である、上記ゴム含有多段重合体(I)の製造方法。 - 下記の(5)~(7)を満たす、請求項14に記載のゴム含有多段重合体(I)の製造方法;
(5):弾性重合体(A)中の、単量体(a1)単位と単量体(a2)単位の合計の含有率が80質量%以上、
(6):弾性重合体(A)中の、単量体(a1)単位/単量体(a2)単位の比率が、50~100質量%/0~50質量%、
(7):硬質重合体(B)中の、単量体(b)単位の含有率が70質量%以上。 - 請求項14又は15に記載の製造方法で得たゴム含有多段重合体(I)。
- 請求項16に記載のゴム含有多段重合体(I)を含有する、アクリル樹脂組成物。
- 請求項1又は17に記載のアクリル樹脂組成物を成形して得た成形体。
- 請求項1又は17に記載のアクリル樹脂組成物を成形して得たアクリル樹脂フィルム。
- 請求項1又は17に記載のアクリル樹脂組成物をカレンダー加工により製膜するアクリル樹脂フィルムの製造方法。
- 請求項19に記載のアクリル樹脂フィルムを基材に積層した積層体。
- 請求項19に記載のアクリル樹脂フィルムを金属部材に積層した積層体。
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CN109661423B (zh) * | 2016-09-22 | 2021-08-24 | 罗门哈斯公司 | 含有磷酸盐的聚合物组合物 |
KR102363660B1 (ko) | 2016-09-22 | 2022-02-16 | 롬 앤드 하아스 컴패니 | 인산염 함유 중합체 조성물 |
WO2018131594A1 (ja) | 2017-01-12 | 2018-07-19 | 三菱ケミカル株式会社 | 積層フィルム及びその製造方法、並びに積層体 |
JP2021517919A (ja) * | 2018-03-29 | 2021-07-29 | ローム アンド ハース カンパニーRohm And Haas Company | 改変スチレンアクリロニトリル |
WO2020203956A1 (ja) * | 2019-03-29 | 2020-10-08 | 大日本印刷株式会社 | 化粧シート、化粧材及び樹脂組成物 |
US11958994B2 (en) | 2019-03-29 | 2024-04-16 | Dai Nippon Printing Co., Ltd. | Sheet, ornamental material, and resin composition |
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EP3130637A4 (en) | 2017-06-14 |
EP3130637A1 (en) | 2017-02-15 |
CN106170514B (zh) | 2021-11-26 |
IL248194B (en) | 2020-08-31 |
CN106170514A (zh) | 2016-11-30 |
JP6716916B2 (ja) | 2020-07-01 |
IL248194A0 (en) | 2016-11-30 |
JPWO2015156323A1 (ja) | 2017-04-13 |
KR20180051665A (ko) | 2018-05-16 |
US20170114215A1 (en) | 2017-04-27 |
KR20160130812A (ko) | 2016-11-14 |
EP3130637B1 (en) | 2022-08-10 |
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