Resin composition and film

Abstract

To provide a resin composition which can suppress thermal deterioration of an additive, and a film containing the same.SOLUTION: A resin composition contains a resin containing a repeating unit having a partial structure represented by the following general formulae (I) or (II) and an additive, wherein a blending ratio of the additive to the resin is 50 mass% or less. In the formula (I), QA represents an ester bond represented in the formula, RA represents a substituent, n1 represents an integer of 1 to 5, * represents a binding site to the balance of the repeating unit, and ** represents a binding site to the phenyl group in the formula. In the formula (II), QB represents a connecting group or a single bond other than the ester bond represented by QA in formula (I), RB represents a substituent, n2 represents an integer of 1 to 5, and * represents a binding site to the balance of the repeating unit, where at least one RB represents a hydroxyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a film. [Background technology]

[0002] Thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, acrylonitrile butadiene styrene resin, and acrylic resin are general-purpose resins used in a variety of everyday items and industrial products due to their good processability. However, these general-purpose resins often have poor heat resistance, making them difficult to use in applications requiring heat resistance. Instead, resins with high melting points, such as engineering plastics and super engineering plastics, are sometimes used. However, these engineering plastics have disadvantages, such as poor processability and low solubility in common organic solvents, making them difficult to use in thin-film applications such as coating films.

[0003] Furthermore, when using resins, it is common to prepare and use resin compositions by mixing various additives with the resin depending on the application, such as to improve processability or weather resistance. For this reason, the additives also need to have heat resistance sufficient to withstand the processing temperature and use temperature of the resin composition. In order to improve the heat resistance of additives, for example, Patent Documents 1 to 3 disclose techniques for increasing the molecular weight of the additives. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-338777 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-40937 [Patent Document 3] International Publication No. 2008 / 062860 Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, various additives with improved heat resistance have been developed, but some additives decompose at high temperatures, making it difficult for them to fully demonstrate their functions. Furthermore, the thermal decomposition products of the additives often accelerate resin degradation. Under these circumstances, there is a need for the development of resin compositions that meet the recent demands for high heat resistance.

[0006] Therefore, an object of the present invention is to provide a resin composition capable of suppressing thermal degradation of additives, and a film containing the same. [Means for solving the problem]

[0007] As a result of intensive research by the present inventors, it was discovered that using a specific resin with excellent heat resistance and further adjusting the compounding ratio of additives to this specific resin within a specific range is important in order to solve the above-mentioned problems, and the present invention was developed based on this finding. The present invention is, for example, as follows.

[0008] [1] A resin composition comprising a resin containing a repeating unit having a partial structure represented by the following general formula (I) or (II) and an additive, wherein the blending ratio of the additive to the resin is 50 mass % or less: [ka] In formula (I), Q A represents the ester bond shown in the formula, and R A represents a substituent, n1 represents an integer of 1 to 5, * represents the bonding site to the rest of the repeating unit, and ** represents the bonding site to the phenyl group in the formula. [ka] In formula (II), Q B is Q in formula (I) A represents a linking group other than an ester bond or a single bond, and R Brepresents a substituent, n2 represents an integer of 1 to 5, and * represents a bonding site with the rest of the repeating unit. B represents a hydroxyl group. [2] The resin composition according to [1], wherein the content of the repeating unit in the resin is 2 mol % or more and 50 mol % or less based on the total repeating units in the resin. [3] The resin composition according to [1] or [2], wherein the repeating unit is any one of a repeating unit derived from a (meth)acrylate monomer, a repeating unit derived from a (meth)acrylamide monomer, and a repeating unit derived from an N-substituted maleimide monomer. [4] The resin composition according to any one of [1] to [3], wherein the resin further contains, in addition to the repeating units, a (meth)acrylate repeating unit having a linear or branched alkyl group having 1 to 5 carbon atoms on the side chain, and / or a (meth)acrylate repeating unit having a hydroxyl group other than a phenolic hydroxyl group on the side chain. [5] The resin composition according to any one of [1] to [3], wherein the resin further contains an olefin-based repeating unit in addition to the repeating unit. [6] The resin composition according to any one of [1] to [3], wherein the resin further contains a halogen atom-containing repeating unit in addition to the repeating unit. [7] A film comprising the resin composition according to any one of [1] to [6]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a resin composition capable of suppressing thermal degradation of additives, and a film containing the same. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The resin composition according to the present embodiment contains a specific resin with excellent heat resistance and an additive, and the additive is blended at a ratio of 50% by mass or less relative to the resin. When a resin with low heat resistance, such as a thermoplastic resin commonly used in daily necessities or industrial products, is used, the thermal decomposition products of the resin accelerate the thermal degradation of the additive used in combination, making it difficult to obtain a resin composition that is excellent in heat resistance and has the desired functions. In the resin composition according to the present embodiment, which contains a specific resin with excellent heat resistance (described in detail below) and an additive whose blending ratio relative to the resin is adjusted to a specific range, the thermal degradation of the additive is suppressed, making it possible to obtain a resin composition that is excellent in heat resistance and has the desired functions.

[0011] <Resin> The resin contained in the resin composition according to this embodiment (hereinafter simply referred to as "resin") contains a repeating unit (hereinafter referred to as "repeating unit (a)") having a partial structure represented by the following general formula (I) or (II):

[0012] [ka]

[0013] In formula (I), Q A represents the ester bond shown in the formula, and R A represents a substituent, n1 represents an integer of 1 to 5, * represents the bonding site to the rest of the repeating unit, and ** represents the bonding site to the phenyl group in the formula.

[0014] R A Examples of the substituent represented by the formula include an alkyl group (e.g., an alkyl group having 1 to 5 carbon atoms), a cycloalkyl group (e.g., a cycloalkyl group having 3 to 6 carbon atoms), an alkoxy group (e.g., a methoxy group or an ethoxy group), a hydroxyl group, an acetyl group, a nitro group, a cyano group, a carboxyl group, an amino group, an ester group, a halogen atom, etc. As mentioned above, n1 represents an integer of 1 to 5, and may be an integer of 1 to 3. When n1 is an integer of 2 or more, a plurality of R Amay be the same or different.

[0015] [ka]

[0016] In formula (II), Q B is Q in formula (I) A represents a linking group other than an ester bond or a single bond, and R B represents a substituent, n2 represents an integer of 1 to 5, and * represents a bonding site with the rest of the repeating unit. B represents a hydroxyl group.

[0017] Q B As mentioned above, Q A represents a linking group other than an ester bond or a single bond, and Q A Examples of linking groups other than the ester bond represented by the formula (II) include -CONR- (where R represents a hydrogen atom or an alkyl group), an alkylene group (for example, an alkylene group having 1 to 4 carbon atoms), a urethane bond, an ether bond, and an ester bond represented by *-O-CO-** (where ** represents the bonding site with the phenyl group in formula (II)).

[0018] R B Examples of the substituent represented by the formula (I) include an alkyl group (e.g., an alkyl group having 1 to 5 carbon atoms), a cycloalkyl group (e.g., a cycloalkyl group having 3 to 6 carbon atoms), an alkoxy group (e.g., a methoxy group, an ethoxy group), a hydroxyl group, an acetyl group, a nitro group, a cyano group, a carboxyl group, an amino group, an ester group, a halogen atom, etc. However, as described above, at least one R B represents a hydroxyl group.

[0019] As described above, n2 represents an integer of 1 to 5, or may be an integer of 1 to 3. When n2 is an integer of 2 or more, a plurality of R B may be the same or different.

[0020] The repeating unit (a) may be any unit as long as it has a partial structure represented by the above-mentioned general formula (I) or (II), and may be, for example, a repeating unit derived from a (meth)acrylate-based monomer, a repeating unit derived from a (meth)acrylamide-based monomer, a repeating unit derived from an N-substituted maleimide-based monomer, or a repeating unit derived from a styrene-based monomer.

[0021] When the repeating unit (a) is a repeating unit derived from a (meth)acrylate monomer, examples of the (meth)acrylate monomer include 4-methoxyphenyl(meth)acrylate, 4-hydroxyphenyl(meth)acrylate, 2,6-di-tert-butylphenyl(meth)acrylate, 2,6-di-tert-butyl-4-methoxyphenyl(meth)acrylate, 2-tert-butyl-4-hydroxyphenyl(meth)acrylate, 3-tert-butyl-4-hydroxyphenyl(meth)acrylate, 2,6-di-tert-butyl-4-methylphenyl(meth)acrylate, 2-hydroxy-4-tert-butylphenyl(meth)acrylate, and 2,4-di-methyl-6-tert-butylphenyl(meth)acrylate.

[0022] When the repeating unit (a) is a repeating unit derived from a (meth)acrylamide-based monomer, examples of the (meth)acrylamide-based monomer include N-(4-hydroxyphenyl)(meth)acrylamide.

[0023] When the repeating unit (a) is a repeating unit derived from an N-substituted maleimide monomer, examples of the N-substituted maleimide monomer include 4-hydroxyphenylmaleimide and 3-hydroxyphenylmaleimide.

[0024] When the repeating unit (a) is a repeating unit derived from a styrene-based monomer, examples of the styrene-based monomer include α-methyl-p-hydroxystyrene.

[0025] In this embodiment, the resin is preferably a di- or ternary copolymer further containing one or more repeating units different from the repeating unit (a). In this case, the content of the repeating unit (a) in the resin is preferably in the range of 2 mol% to 50 mol% based on the total repeating units in the resin. When the content of the repeating unit (a) in the resin is 2 mol% or more, thermal decomposition of the resin and the additives used in combination can be more effectively suppressed.

[0026] Furthermore, when the content of the repeating unit (a) in the resin is 50 mol% or less, the effect of suppressing thermal decomposition of the resin and any additives used in combination can be maintained, while the occurrence of yellowing of the resin when heated and the hardening and brittleness of the resin can be effectively suppressed. From the same viewpoint, the content of the repeating unit (a) in the resin may be 2 mol% or more and 30 mol% or less, or 2 mol% or more and 20 mol% or less.

[0027] In the present embodiment, when the resin is a copolymer, examples of the repeating unit (hereinafter referred to as a "copolymerization component") that may be contained and that is different from the repeating unit (a) include a (meth)acrylate repeating unit, an olefin repeating unit, a halogen atom-containing repeating unit, a styrene repeating unit, a vinyl acetate repeating unit, and a vinyl alcohol repeating unit.

[0028] Examples of the (meth)acrylate repeating unit that is a copolymerization component include a repeating unit derived from a (meth)acrylate monomer having a linear or branched alkyl group on the side chain, and a repeating unit derived from a (meth)acrylate monomer having a hydroxyl group (excluding phenolic hydroxyl groups) on the side chain.

[0029] Examples of the (meth)acrylate repeating unit having a linear or branched alkyl group on the side chain include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and isooctyl (meth)acrylate. Examples of monomer-derived components include 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, and octadecyl (meth)acrylate. These may be used alone or in combination of two or more. Among the above, (meth)acrylate-based repeating units having a linear or branched alkyl group having 1 to 4 carbon atoms in the side chain are preferred.

[0030] Examples of (meth)acrylic repeating units having a hydroxyl group other than a phenolic hydroxyl group in a side chain include components derived from monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0031] Examples of the olefin repeating unit that is a copolymerization component include components derived from olefin monomers such as ethylene, propylene, isoprene, butadiene, etc. These may be used alone or in combination of two or more.

[0032] Examples of the halogen atom-containing repeating unit that is a copolymerization component include components derived from monomers such as vinyl chloride, vinylidene chloride, etc. These may be used alone or in combination of two or more.

[0033] Examples of the styrene repeating unit that is a copolymerization component include components derived from styrene monomers such as styrene, α-methylstyrene, vinyltoluene, etc. These may be used alone or in combination of two or more.

[0034] The copolymer may have any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer structure. If the copolymer has a random copolymer structure, the manufacturing process and preparation with the cyanine dye are easy. Therefore, a random copolymer is preferable to other copolymers.

[0035] Radical polymerization can be used as a polymerization method for obtaining the copolymer. Radical polymerization is preferred because it is easy to produce industrially. Radical polymerization may be a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or the like. For radical polymerization, it is preferable to use a solution polymerization method. By using a solution polymerization method, it is easy to control the molecular weight of the copolymer.

[0036] In the radical polymerization, the above-mentioned monomer may be diluted with a polymerization solvent, and then a polymerization initiator may be added to polymerize the monomer. Examples of the polymerization solvent include ester-based solvents, alcohol ether-based solvents, ketone-based solvents, aromatic solvents, amide-based solvents, and alcohol-based solvents. Examples of the ester-based solvent include methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl lactate, and ethyl lactate. Examples of the alcohol ether-based solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-methyl-1-butanol. Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the aromatic solvent include benzene, toluene, and xylene. Examples of the amide-based solvent include formamide and dimethylformamide. The alcohol solvent may be, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, diacetone alcohol, 2-methyl-2-butanol, etc. The above-mentioned polymerization solvents may be used alone or in combination of two or more.

[0037] In radical polymerization, the amount of polymerization solvent used is not particularly limited. When the total amount of monomers is set to 100 parts by mass, the amount of polymerization solvent used is preferably 1 part by mass or more and 1,000 parts by mass or less, and more preferably 10 parts by mass or more and 500 parts by mass or less.

[0038] The radical polymerization initiator may be, for example, a peroxide or an azo compound. The peroxide may be, for example, benzoyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, or di-t-butyl peroxide. The azo compound may be, for example, azobisisobutyronitrile, azobisamidinopropane salt, azobiscyanovaleric acid (salt), or 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide].

[0039] The amount of radical polymerization initiator used is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 15 parts by mass, and even more preferably 0.005 to 10 parts by mass, when the total amount of monomers is set to 100 parts by mass. The radical polymerization initiator may be added to the monomers and polymerization solvent before the start of polymerization, or may be added dropwise to the polymerization reaction system. Adding the radical polymerization initiator dropwise to the monomers and polymerization solvent in the polymerization reaction system is preferred because it can suppress heat generation due to polymerization.

[0040] The reaction temperature for radical polymerization is appropriately selected depending on the types of radical polymerization initiator and polymerization solvent, and is preferably 60° C. or higher and 110° C. or lower from the viewpoints of ease of production and reaction controllability.

[0041] <Additives> The resin composition according to this embodiment contains the additive in a blending ratio of 50% by mass or less relative to the resin, in order to achieve the effect of suppressing thermal degradation of the additive by using a resin containing the repeating unit (a) and having excellent heat resistance. The blending ratio of the additive to the resin may be 30% by mass or less, or may be 10% by mass or less. The lower limit of the blending ratio of the additive can be appropriately set depending on the purpose of use of the additive, the desired function, etc., and is not particularly limited. For example, the lower limit of the blending ratio of the additive may be 0.01% by mass or more. The resin composition according to this embodiment may contain one type of additive alone, or may contain two or more types. When the resin composition according to this embodiment contains two or more types of additives, the blending ratio indicates the total mass ratio of the additives to the resin.

[0042] In this embodiment, the additive refers to an organic additive that is added to the resin at the above-mentioned blending ratio for the purpose of maintaining the function of the resin or imparting a new function. Here, the "organic additive" is an additive selected from compounds containing carbon atoms, and may be a low molecular weight compound, a high molecular weight compound, an oligomer, or an organic metal salt. However, the additive is assumed to not chemically react with the resin and to exist in the composition with the same chemical structure as when added, and does not include crosslinking agents or curing agents that crosslink resin chains with heat or light. Specific examples of additives are shown in Table 1.

[0043] [Table 1-1]

[0044] [Table 1-2]

[0045] The resin composition according to this embodiment can be suitably used in various applications requiring heat resistance, such as thin film applications such as coating films, film substrates, and adhesive layers used to bond film substrates together. Examples include gas barrier films for packaging materials for food, medical supplies, medicines, etc., optical films used in security products with anti-counterfeiting structures, coating films (surface protective layers) used in building material sheets such as decorative sheets, and color filters used in liquid crystal displays, etc. [Example]

[0046] <Synthesis of resin (group a)> Synthesis Example 1: Synthesis of Resin P-1a 80 parts by weight of cyclohexanone was prepared as a polymerization solvent. 85 parts by weight of methyl methacrylate (MMA) and 15 parts by weight of 4-methoxyphenyl methacrylate (MPhMA) were prepared as acrylic monomers. 0.22 parts by weight of benzoyl peroxide (BPO) was prepared as a polymerization initiator. These were placed in a reaction vessel equipped with a stirrer and a reflux condenser. While introducing nitrogen gas into the reaction vessel, the mixture was stirred and refluxed for 8 hours while heated to 80°C. This yielded a polymer solution containing an acrylic copolymer formed from repeating units derived from MMA and repeating units derived from MPhMA. The resulting polymer solution was added dropwise to a large amount of methanol for reprecipitation purification, and then dried under reduced pressure at room temperature for 24 hours to obtain Resin P-1a, which will be described later.

[0047] Synthesis of Resin P-2a Resin P-2a shown below was obtained in the same manner as in Synthesis Example 1, except that 4-hydroxyphenyl methacrylate (HPMA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0048] Synthesis of Resin P-3a Resin P-3a shown below was obtained in the same manner as in Synthesis Example 1, except that N-(4-hydroxyphenyl)methacrylamide (HPMAA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0049] Synthesis of Resin P-4a Resin P-4a shown below was obtained in the same manner as in Synthesis Example 1, except that 4-hydroxymaleimide (HPhMI) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0050] Synthesis of Resin P-101a For comparison, Resin P-101a shown below was obtained in the same manner as in Synthesis Example 1, except that 4-methoxyphenyl methacrylate (MPhMA) was not used.

[0051] Synthesis of Resin P-102a For comparison, Resin P-102a shown below was obtained in the same manner as in Synthesis Example 1, except that phenyl methacrylate (PhMA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0052] Synthesis of Resin P-103a For comparison, Resin P-103a shown below was obtained in the same manner as in Synthesis Example 1, except that styrene (St) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0053] [ka]

[0054] <Evaluation> (Evaluation 1) Resin heat resistance evaluation The mass loss rate (%) of each resin synthesized above under air and nitrogen atmospheres was measured using the following method. A differential scanning calorimeter / thermogravimetric simultaneous analyzer (STA7000, manufactured by Hitachi High-Tech Science Corporation) was used to measure the mass loss rate (%). The sample was heated at 250°C for 20 minutes under air or nitrogen atmosphere, and the mass loss (M = M0 - M1) calculated by subtracting the mass after heating (M1) from the initial mass before heating (M0) was divided by the initial mass (M0) to calculate the mass loss rate ([M / M0] x 100) (%). The lower the mass loss rate, the better the heat resistance.

[0055] A mass loss rate of less than 20% in both air and nitrogen atmosphere measurements was rated as "A," and a mass loss rate of 20% or more in either or both air and nitrogen atmosphere measurements was rated as "B." The results are shown in Table 2.

[0056] (Evaluation 2) Evaluation of additives' ability to suppress thermal degradation A resin solution was prepared by dissolving 20 parts by weight of the obtained resin in 80 parts by weight of cyclohexanone. To the obtained resin solution, 0.1 parts by weight of a hindered amine light stabilizer (trade name: Tinuvin (registered trademark) 123, manufactured by BASF Japan Ltd.) or a cyanine dye having the structure shown in the following formula (1) and tris(pentafluoroethyl)trifluorophosphate (FAP) as a counter anion was added as an additive to obtain a resin solution. The resin solution was applied to a glass substrate using spin coating, and then heated and dried for 10 minutes on a hot plate set at 200°C to form a 1 μm-thick coating film.

[0057] The glass substrate on which the coating film was formed was heated at 250°C for 10 minutes, and the residual rate of the additive in the coating film was measured. 2The glass substrate was cut into pieces of 100 mm in size, immersed in 1.5 mL of acetone, and extracted in an ultrasonic cleaner for 60 minutes. The additives in the glass substrate extract were quantified using ultra-high performance liquid chromatography / mass spectrometry (UHPLC / MS) (Ultra-high performance liquid chromatograph / mass spectrometer (UHPLC / MS), Agilent 1260 LC System / 6130B Single Quad MS System). The additive remaining rate ([V1 / V0] x 100) (%) was calculated by dividing the amount of additive remaining after heating (V1) by the initial amount of additive before heating (V0). The higher the additive remaining rate, the better the additive's ability to suppress thermal degradation.

[0058] In both measurements of the resin composition containing the hindered amine light stabilizer and the resin composition containing the cyanine dye, the residual additive rate of 90% or more was evaluated as "A," and the residual additive rate of less than 90% in either or both measurements was evaluated as "B." The results are shown in Table 2.

[0059] [ka]

[0060] [Table 2]

[0061] <Synthesis of resin (group b)> Synthesis Example 2: Synthesis of Resin P-1b A 300 mL autoclave reactor was prepared, and 20 mL of a 50% by mass solution of 4-methoxyphenyl methacrylate (MPhMA) in methanol and 1 g of t-butyl hydroperoxide as a polymerization initiator were added and dissolved. After degassing the reactor, ethylene gas was introduced into the reactor to produce a copolymer at a pressure of 100 bar and a polymerization temperature of 175°C. The resulting copolymer was dissolved in xylene and purified by reprecipitation with methanol to obtain Resin P-1b, which will be described later.

[0062] Synthesis of Resin P-2b Resin P-2b shown below was obtained in the same manner as in Synthesis Example 2, except that 4-hydroxyphenyl methacrylate (HPMA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0063] Synthesis of Resin P-101b For comparison, Resin P-101b shown below was obtained in the same manner as in Synthesis Example 2, except that 4-methoxyphenyl methacrylate (MPhMA) was not used.

[0064] Synthesis of Resin P-102b For comparison, Resin P-102b shown below was obtained in the same manner as in Synthesis Example 2, except that benzyl methacrylate (BzMA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0065] [ka]

[0066] (Evaluation 3) Resin heat resistance evaluation The heat resistance of each of the resins synthesized above was evaluated in the same manner as in Evaluation 1. The results are shown in Table 3.

[0067] (Evaluation 4) Evaluation of additives' ability to suppress thermal degradation One gram of each resin synthesized above was mixed with 0.01 g of a hindered amine light stabilizer (product name: Tinuvin 123, manufactured by BASF Japan Ltd.) or 0.01 g of a cyanine dye having tris(pentafluoroethyl)trifluorophosphate (FAP) as a counter anion, as shown in formula (1). The resulting resin-additive mixture was placed on a glass substrate, and the glass substrate was heated on a hot plate at 200°C for 10 minutes. An aluminum block heated to 200°C was placed on the molten mixture and pressed with a force of 20 kgf for 10 seconds, then rapidly cooled to room temperature. The pressed sheet-like mixture was peeled off from the glass substrate, immersed in 1.5 mL of acetone, and extracted in an ultrasonic cleaner for 60 minutes. The amount of additives in the glass substrate extract was quantified using ultra-high performance liquid chromatography / mass spectrometry (UHPLC / MS) (Ultra-high performance liquid chromatograph / mass spectrometer (UHPLC / MS), Agilent 1260 LC System / 6130B Single Quad MS System). The additive remaining rate ([V1 / V0] x 100) (%) was calculated by dividing the amount of additive remaining after heating (V1) by the initial amount of additive before heating (V0). The higher the additive remaining rate, the better the additive's ability to suppress thermal degradation.

[0068] In both measurements of the resin composition containing the hindered amine light stabilizer and the resin composition containing the cyanine dye, the residual additive rate of 90% or more was evaluated as "A," and the residual additive rate of less than 90% in either or both measurements was evaluated as "B." The results are shown in Table 3.

[0069] [Table 3]

[0070] <Synthesis of resin (group c)> Synthesis Example 3: Synthesis of Resin P-1c A 300 mL autoclave reactor was prepared and dissolved in 0.1 g of potassium persulfate, 1.0 g of sodium lauryl sulfate, 12 mL of a 10% aqueous solution of partially saponified polyvinyl alcohol (degree of polymerization 500, degree of saponification 98.6%), and 50 mL of water. 25 g of vinyl chloride monomer was added and the mixture was allowed to react at 45°C for 7 hours to obtain an emulsion solution. The emulsion solution was freeze-dried to recover the polyvinyl chloride precipitate, which was washed with warm water and then dried under reduced pressure. The resulting powder was dissolved in tetrahydrofuran, and the insoluble polyvinyl alcohol was removed by filtration. This tetrahydrofuran solution was poured into a large amount of methanol, and the precipitate was filtered to obtain polyvinyl chloride (PVC).

[0071] 0.8 g of the obtained PVC was dissolved in 10 mL of cyclohexanone, and 0.2 g of 4-hydroxyphenyl methacrylate (HPMA) and 0.02 g of benzoyl peroxide were added, followed by a reaction at 80°C for 8 hours under a nitrogen atmosphere. The resulting reaction solution was poured into a large amount of methanol, and the precipitate was filtered off to obtain polyvinyl chloride graft copolymer P-1c containing the repeating unit shown below.

[0072] Synthesis of Resin P-2c A polyvinyl chloride graft copolymer P-2c containing the repeating unit shown below was obtained in the same manner as in Synthesis Example 3, except that N-(4-hydroxyphenyl)methacrylamide (HPMAA) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0073] Synthesis of Resin P-3c A polyvinyl chloride graft copolymer P-3c containing the repeating unit shown below was obtained in the same manner as in Synthesis Example 3, except that 4-methoxyphenyl methacrylate was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0074] Synthesis of Resin P-101c For comparison, a polyvinyl chloride graft copolymer P-101c containing the repeating unit shown below was obtained in the same manner as in Synthesis Example 3, except that vinyl acetate (VAc) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0075] Synthesis of Resin P-102c For comparison, polyvinyl chloride graft copolymer P-102c containing the repeating unit shown below was obtained in the same manner as in Synthesis Example 3, except that methyl methacrylate (MMA) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0076] [ka]

[0077] <Evaluation> (Evaluation 5) Resin heat resistance evaluation For each of the resins synthesized above, the mass loss rate ([M / M0]×100) (%) was measured in an air atmosphere and a nitrogen atmosphere using the same method as in Evaluation 1.

[0078] A mass loss rate of less than 30% in both air and nitrogen atmosphere measurements was rated as "A," and a mass loss rate of 30% or more in either or both air and nitrogen atmosphere measurements was rated as "B." The results are shown in Table 4.

[0079] (Evaluation 6) Evaluation of additives' ability to suppress thermal degradation 1 g of each polyvinyl chloride graft copolymer was dissolved in 10 g of a 7:3 toluene:cyclohexanone solution to prepare a polymer solution. This polymer solution was mixed with 0.01 g of a hindered amine light stabilizer (product name: Tinuvin 123, manufactured by BASF Japan Ltd.) or a cyanine dye having tris(pentafluoroethyl)trifluorophosphate (FAP) as a counter anion, as shown in formula (1), to prepare a resin solution. The resin solution was applied to a glass substrate using a spin coater and dried by heating on a hot plate set at 200°C for 10 minutes to form a 1 μm-thick coating film.

[0080] The glass substrate on which the coating film was formed was heated at 250°C for 10 minutes, and the residual rate of the additive in the coating film was measured. 2 The glass substrate was cut into pieces of 100 mm in size, immersed in 1.5 mL of acetone, and extracted in an ultrasonic cleaner for 60 minutes. The additives in the glass substrate extract were quantified using ultra-high performance liquid chromatography / mass spectrometry (UHPLC / MS) (Ultra-high performance liquid chromatograph / mass spectrometer (UHPLC / MS), Agilent 1260 LC System / 6130B Single Quad MS System). The additive remaining rate ([V1 / V0] x 100) (%) was calculated by dividing the amount of additive remaining after heating (V1) by the initial amount of additive before heating (V0). The higher the additive remaining rate, the better the additive's ability to suppress thermal degradation.

[0081] In both measurements of the resin composition containing the hindered amine light stabilizer and the resin composition containing the cyanine dye, the residual additive rate of 80% or more was evaluated as "A," and the residual additive rate of less than 80% in either or both measurements was evaluated as "B." The results are shown in Table 4.

[0082] [Table 4]

[0083] <Synthesis of resin (group d)> Synthesis Example 4: Synthesis of Resin P-1d 80 parts by weight of cyclohexanone was prepared as a polymerization solvent. Also, 13 parts by weight of methyl methacrylate (MMA), 4 parts by weight of 2-hydroxyethyl methacrylate (HEMA), and 3 parts by weight of 4-hydroxyphenyl methacrylate (HPMA) were prepared as acrylic monomers. Furthermore, 0.22 parts by weight of benzoyl peroxide (BPO) was prepared as a polymerization initiator. These were placed in a reaction vessel equipped with a stirrer and a reflux condenser. While introducing nitrogen gas into the reaction vessel, the mixture was stirred and refluxed for 8 hours while heating to 80°C. This yielded a polymer solution containing the resin (acrylic copolymer) P-1d shown below, which is formed from repeating units derived from MMA, HEMA, and HPMA.

[0084] Synthesis of Resin P-2d A polymer solution containing the resin P-2d described below was obtained in the same manner as in Synthesis Example 4, except that N-(4-hydroxyphenyl)methacrylamide (HPMAA) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0085] Synthesis of resin P-3d A polymer solution containing Resin P-3d described below was obtained in the same manner as in Synthesis Example 4, except that 4-hydroxyphenylmaleimide (4-HPhMI) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0086] Synthesis of resin P-4d A polymer solution containing Resin P-4d described below was obtained in the same manner as in Synthesis Example 4, except that 3-hydroxyphenylmaleimide (3-HPhMI) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0087] Synthesis of resin P-5d A polymer solution containing Resin P-5d described below was obtained in the same manner as in Synthesis Example 4, except that 4-methoxyphenyl methacrylate (MPhMA) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0088] Synthesis of Resin P-6d A polymer solution containing Resin P-6d described below was obtained in the same manner as in Synthesis Example 4, except that 2,6-di-tert-butylphenyl methacrylate (t-BuPhMA) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0089] Synthesis of Resin P-7d A polymer solution containing Resin P-7d described below was obtained in the same manner as in Synthesis Example 4, except that 2,6-di-tert-butyl-4-methoxyphenyl methacrylate (t-BuMPhMA) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0090] Synthesis of Resin P-101d For comparison, a polymer solution containing the below-described resin P-101d was obtained in the same manner as in Synthesis Example 4, except that phenyl methacrylate (PhMA) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0091] Synthesis of Resin P-102d For comparison, a polymer solution containing the resin P-102d described below was obtained in the same manner as in Synthesis Example 4, except that N-phenylmethacrylamide (PhMAA) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0092] Synthesis of Resin P-103d For comparison, a polymer solution containing the following resin P-103d was obtained in the same manner as in Synthesis Example 4, except that N-phenylmaleimide (PhMI) was used instead of 4-hydroxyphenyl methacrylate (HPMA).

[0093] [ka]

[0094] <Making decorative sheets> A resin composition was obtained by adding 0.5 parts by mass of Tinuvin 326 (BASF Japan Ltd.) as an ultraviolet absorber, 0.4 parts by mass of Tinuvin 622 (BASF Japan Ltd.) as a light stabilizer, and 0.1 parts by mass of Chimassorb 2020 (BASF Japan Ltd.) to 100 parts by mass of a transparent homopolypropylene resin (Prime PP; Prime Polymer Co., Ltd.). This resin composition was melt-extruded to obtain a polypropylene resin film with a thickness of 80 μm.

[0095] A wood grain pattern was gravure printed onto a 70-μm-thick polyethylene sheet using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to form a 3-μm-thick pattern layer, which was then dry-laminated onto the substrate with the polypropylene resin film using a 2-μm-thick adhesive (Takelac A540; manufactured by Mitsui Chemicals, Inc.).

[0096] A polymer solution containing each of the resins (acrylic copolymers) obtained above was applied to the polypropylene resin film of the laminate using a bar coater to a layer thickness of 8 μm, followed by drying to form a surface protective layer, thereby obtaining a decorative sheet. Four types of polymer solutions were prepared for each resin as the polymer solution for the surface protective layer. Specifically, four types of polymer solutions were prepared: the polymer solution itself containing the resin obtained above, and a polymer solution prepared by adding xylylene diisocyanate (XDI) (trade name: Takenate® 500; manufactured by Mitsui Chemicals, Inc.) as a curing agent in a solids mass ratio of resin:curing agent of 7:3. Each solution was prepared with or without a hindered amine light stabilizer (trade name: Tinuvin 123; manufactured by BASF Japan, Ltd.) added as an additive.

[0097] <Evaluation> (Evaluation 7) Heat resistance evaluation of the surface protection layer The mass loss rate (%) of the surface protective layer in an air atmosphere was measured using the following method. A differential thermal and gravimetric simultaneous analyzer (STA7000, manufactured by Hitachi High-Tech Science Corporation) was used to measure the mass loss rate (%). 5 mg of the surface protective layer was scraped off from the decorative sheet obtained above and placed in an aluminum pan to prepare a measurement sample. This sample was heated at 250°C for 20 minutes in an air atmosphere, and the mass loss rate ([M / M0] x 100) (%) was calculated by subtracting the mass after heating (M1) from the initial mass before heating (M0) to obtain the mass loss amount (M = M0 - M1), which was then divided by the initial mass (W0). The lower the mass loss rate, the better the heat resistance.

[0098] A mass loss rate of less than 20% was rated as "A," and a mass loss rate of 20% or more was rated as "B." The results are shown in Table 5.

[0099] (Evaluation 8) Evaluation of additives' ability to suppress thermal degradation 1cm of the decorative sheet obtained above 2 A sample was cut out and heated at 250°C for 20 minutes in air to prepare a sample, which was then immersed in 1.5 mL of acetone and extracted in an ultrasonic cleaner for 60 minutes. The additives in the decorative sheet extract were quantified using ultra-high performance liquid chromatography / mass spectrometry (UHPLC / MS) (Ultra-high performance liquid chromatograph / mass spectrometer (UHPLC / MS), Agilent 1260 LC System / 6130B Single Quad MS System). In addition, the above-mentioned film laminate without a surface protective layer was prepared and cut into 1 cm pieces in the same manner as above. 2 The film was cut out, subjected to the same heat treatment and extraction procedures as above, and the amount of additives in the extract of the film laminate was determined. The amount of additive in the surface protective layer of the decorative sheet was determined by taking the difference between the amount of additive in the extract of the decorative sheet and the amount of additive in the extract of the film laminate.

[0100] The additive remaining rate ([V1 / V0] x 100) (%) was calculated by dividing the amount of additive remaining after heating (V1) by the initial amount of additive before heating (V0). The higher the additive remaining rate, the better the additive's ability to suppress thermal degradation. An additive remaining rate of 90% or more was rated "A," and an additive remaining rate of less than 90% was rated "B." The results are shown in Table 5.

[0101] [Table 5-1]

[0102] [Table 5-2]

[0103] [Table 5-3]

[0104] [Table 5-4]

[0105] [Table 5-5]

[0106] The present invention is not limited to the above-described embodiments, and various modifications can be made in the implementation stage without departing from the spirit of the invention. Furthermore, the embodiments may be implemented in appropriate combinations, in which case the combined effects can be obtained. Furthermore, the above-described embodiments include various inventions, and various inventions can be extracted by combining selected elements from the disclosed elements. For example, if the problem can be solved and the desired effect can be obtained even if some elements are deleted from all elements shown in the embodiments, the configuration from which these elements are deleted can be extracted as an invention.

Claims

1. The repeating unit (a) is a (meth)acrylate repeating unit (aI) represented by the following general formula (i), or a (meth)acrylamide repeating unit (aII) represented by the following general formula (iii) or an N-substituted maleimide repeating unit (aII) represented by the following general formula (ii), an olefinic repeating unit (d) derived from an olefinic monomer selected from ethylene, propylene, isoprene, and butadiene; The composition contains a resin containing the compound and an additive, the content of the repeating unit (a) is 2 mol % or more and 20 mol % or less based on all repeating units in the resin, A resin composition in which the blending ratio of the additive to the resin is 50 mass % or less. 【Chemical 1】 In formula (i), R represents a hydrogen atom or a methyl group, and R Ａ represents a substituent, and n1 represents an integer of 1 to 5. 【Chemistry 2】 In formula (ii), R Ｂ represents a substituent, and n2 represents an integer of 1 to 5. However, at least one R Ｂ represents a hydroxyl group. 【Chemistry 3】 In formula (iii), R represents a hydrogen atom or a methyl group, and R Ｂ represents a substituent, and n2 represents an integer of 1 to 5. However, at least one R Ｂ represents a hydroxyl group.

2. The resin composition according to claim 1 , wherein the repeating unit (d) is a repeating unit represented by the following formula (d): 【Chemistry 4】

3. The repeating unit (a) is a (meth)acrylate repeating unit (aI) represented by the following general formula (i), or a (meth)acrylamide repeating unit (aII) represented by the following general formula (iii) or an N-substituted maleimide repeating unit (aII) represented by the following general formula (ii), a halogen atom-containing repeating unit (e) derived from a monomer selected from vinyl chloride and vinylidene chloride; The composition contains a resin containing the compound and an additive, the content of the repeating unit (a) is 2 mol % or more and 20 mol % or less based on all repeating units in the resin, A resin composition in which the blending ratio of the additive to the resin is 50 mass % or less. 【Chemistry 5】 In formula (i), R represents a hydrogen atom or a methyl group, and R Ａ represents a substituent, and n1 represents an integer of 1 to 5. 【Chemistry 6】 In formula (ii), R Ｂ represents a substituent, and n2 represents an integer of 1 to 5. However, at least one R Ｂ represents a hydroxyl group. 【Chemistry 7】 In formula (iii), R represents a hydrogen atom or a methyl group, and R Ｂ represents a substituent, and n2 represents an integer of 1 to 5. However, at least one R Ｂ represents a hydroxyl group.

4. The resin composition according to claim 3 , wherein the repeating unit (e) is a repeating unit represented by the following formula (e): 【Chemistry 8】

5. The resin composition according to any one of claims 1 to 4, wherein the (meth)acrylate repeating unit (aI) represented by the general formula (i) contains a (meth)acrylate repeating unit represented by the following general formula (aI"): 【Chemistry 9】 In formula (aI"), R represents a hydrogen atom or a methyl group.

6. A film comprising the resin composition according to claim 1 .

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